Polyester based cobalt concentrates for oxygen scavenging compositions

ABSTRACT

A solid concentrate is provided having a combination of a transition metal present in an amount ranging from 1,000 to 40,000 ppm (weight by metal) and a polyester polymer present in an amount of at least 40 wt. % based on the weight of the concentrate. Concentrates made with highly modified polyester polymers are easy to compound with transition metals forming less brittle polymer upon melt extrusion. Bottle preforms and oxygen scavenging bottles can be made from these concentrates by combining solid polyester particles, solid polyamide particles, and solid these concentrate particles c into an melt processing zone, forming a melt, and forming an article directly from the melt. The b* color and the L* color and the haze levels of the preforms are improved over the preforms made with liquid carriers instead of solid concentrates. The particles are also advantageously simultaneously dried in a drying zone under conditions effective to at least partially remove moisture from the blend to thereby further improve the b* color and L* color.

CROSS REFERENCES TO RELATED APPLICATIONS

This application is a continuation application of U.S. application Ser.No. 11/292,441, filed Dec. 2, 2005, which claims the benefit of U.S.Provisional Application Ser. No. 60/633,524 filed Dec. 6, 2004, fullyincorporated herein by reference.

FIELD OF THE INVENTION

The invention pertains to the manufacture of polyester preforms andbottles, and more particularly to a concentrate containing at least apolyethylene terephthalate polymer and cobalt, useful for providingoxygen scavenging compositions, preforms, bottles and other articles.

BACKGROUND OF THE INVENTION

Packaging for food, beverages and in particular beer and fruit juices,cosmetics, medicines, and the like are sensitive to oxygen exposure andrequire high barrier properties to oxygen and carbon dioxide to preservethe freshness of the package contents and avoid changes in flavor,texture and color. Blends containing small amounts of high barrierpolyamides, such as poly(m-xylylene adipamide), typically knowncommercially as MXD6, with polyesters such as poly(ethyleneterephthalate), PET, enhance the passive barrier properties of PET.

To further reduce the entry of oxygen into the contents of the package,small amounts of transition metal salts, such as cobalt salts, can beadded to the blend of PET and polyamide to catalyze and actively promotethe oxidation of the polyamide polymer, thereby further enhancing theoxygen barrier characteristics of the package. The use of such activeoxygen scavengers, which chemically remove oxygen migrating through thewalls of the package, can be a very effective method to reduce theoxygen transmission rates of plastics used in packaging. While currentlyavailable scavengers have found some utility, they also suffer from avariety of drawbacks that include lengthy induction periods before fullactivity is achieved and/or life spans (capacities) which are too short.In some instances, these deficiencies can be partially addressed byincreasing the level of oxygen scavenger in the package structure.However, this typically increases the cost of the final package andproduces undesirable effects on the appearance of the package, such asadding haze or color. In addition, increasing the concentration of theoxygen scavenger can complicate manufacture and recycling of thepackage. Thus, there is a need for improved oxygen scavenging materialsthat rapidly achieve high scavenging rates.

Transition metal salts have been added to PET polymers and to blends ofPET polymers with polyamide polymers to impart active oxygen scavengingactivity. Typical methods for incorporating these metal salts into thePET composition include feeding the metal contained in a liquid carrierinto an extruder along with a feed of bulk PET pellets. Alternatively, ametal such as cobalt is frequently added to a melt phase process for theproduction of PET, such that the PET pellets already contain cobalt whenfed to the extruder. In this method, the metal salts can be added in lowconcentrations corresponding to the desired concentration in thearticle, or in higher concentrations to form a masterbatch. However,adding metal salts to a melt phase process for making the polymer mayresult in discoloration or the generation of excessive levels of otherundesirable byproducts such as diethylene glycol and acetaldehyde at thehigh temperature conditions and long residence times employed in a PETpolymerization reactor. This condition is exacerbated if the metal isadded early or the residence time of the polymer melt containing thetransition metal is lengthy.

We have found that deficiencies in the oxygen scavenging activity arepartly attributable to the form in which the transition metal is addedto PET. We have also found that when cobalt is added to a bulk polyesterpolymer in a form of a solid concentrate comprising a polyester carrier,a number of advantages are realized.

SUMMARY OF THE INVENTION

There is now provided a solid concentrate obtained by melt compounding atransition metal in an amount ranging from 1000 ppm to 40,000 ppm (bymetal) and a polyester polymer having an It.V. of at least 0.55 dL/g inan amount of at least 40 wt. %, each based on the weight of theconcentrate. By melt compounding, one has greater flexibility to usepolyester polymers with higher IV to compensate for IV breakdown undermelt conditions, to provide for a short residence time of the metal inthe melt, and to make a blend under milder conditions that is typicallyencountered in a finisher or final reactor for making the polymer.Articles made from the concentrates of the invention may also moreeffectively scavenge oxygen compared to articles made from polyesterpolymers to which the transition metal was added in the melt phase.There is also provided a process for the manufacture of a preformcomprising combining solid polyester particles comprising polyesterpolymers, solid polyamide particles comprising polyamide polymers, and asolid concentrate obtained by melt compounding a transition metalcompound in an amount ranging from 1000 ppm to 40,000 ppm and apolyester polymer having an It.V. of at least 0.55 dL/g in an amount ofat least 40 wt. %, each based on the weight of the concentrate, into amelt processing zone, forming a melt, and forming an article directlyfrom the melt.

There is also provided a drying process, comprising simultaneouslydrying in a drying zone a blend comprising solid polyester particlescomprising polyester polymers, solid polyamide particles comprisingpolyamide polymers, and a solid concentrate comprising a polyesterpolymer and a transition metal present in an amount ranging from 1000ppm to 40,000, under conditions effective to at least partially removemoisture from the blend.

There is further provided a solid concentrate comprising a polyesterpolymer concentrate comprising a transition metal in an amount of atleast 1000 ppm, and polyester polymers in an amount of least 40 wt. %,each based on the weight of the concentrate, wherein at least a portionof the polyester polymers comprise highly modified polyester polymerscontaining hydroxyl modifier residues in an amount ranging from 20 mole% to 60 mole %, based on the all the moles of hydroxyl compound residuespresent in the polyester polymer and/or polycarboxylic acid modifiers inan amount ranging from 20 mole % to 60 mole %, based on all the moles ofpolycarboxylic acid residues present in the polyester polymer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graphical illustration of the oxygen transmission rate overtime of bottles made from compositions of the invention compared toresin compositions in which the cobalt was added by other means

FIG. 2 is a graphical illustration of the oxygen transmission rate overtime of bottles made from various compositions encompassed by theinvention

FIG. 3 is a graphical illustration of the oxygen transmission rate overtime of bottles made from additional compositions encompassed by theinvention

FIG. 4 is a also graphical illustration of the oxygen transmission rateover time of bottles made from additional compositions encompassed bythe invention

FIG. 5 is a graphical illustration of the long term preformance of theoxygen transmission rate over time of bottles made from additionalcompositions encompassed by the invention

FIG. 6 is a graphical illustration of the oxygen transmission rate overtime of bottles made from compositions in which cobalt was added to thepolyester during the melt polymerization step

FIG. 7 is a graphical illustration of the oxygen transmission rate overtime of bottles made from compositions of the invention compared to aresin composition in which the cobalt was added via a liquid concentrate

FIG. 8 is a graphical illustration of the oxygen transmission rate overtime of bottles made from additional compositions of the inventioncompared to a resin composition in which the cobalt was added via aliquid concentrate

FIG. 9 is a graphical illustration of the oxygen transmission rate overtime of additional bottles made from compositions of the inventioncompared to resin compositions in which the cobalt was via liquidconcentrates

FIG. 10 is a graphical illustration of the oxygen partial pressure overtime in sealed ampoules containing compositions of the invention inwhich the components of the blend were “Codried” compared to similarcompositions in which the components were not dried together prior tothe injection molding step

DETAILED DESCRIPTION OF THE INVENTION

The present invention may be understood more readily by reference to thefollowing detailed description of the invention.

It must also be noted that, as used in the specification and theappended claims, the singular forms “a,” “an” and “the” include pluralreferents unless the context clearly dictates otherwise. For example,reference to processing or making a “polymer,” a “preform,” “article,”“container,” “concentrate” or “bottle” is intended to include theprocessing or making of a plurality of polymers, preforms, articles,containers or bottles. References to a composition containing “an”ingredient or “a” polymer is intended to include other ingredients orother polymers, respectively, in addition to the one named.

By “comprising” or “containing” or “obtained by” is meant that at leastthe named compound, element, particle, or method step etc. must bepresent in the composition or article or method, but does not excludethe presence of other compounds, catalysts, materials, particles, methodsteps, etc., even if the other such compounds, material, particles,method steps etc. have the same function as what is named, unlessexpressly excluded in the claims.

It is also to be understood that the mention of one or more method stepsdoes not preclude the presence of additional method steps before orafter the combined recited steps or intervening method steps betweenthose steps expressly identified. Moreover, the lettering of processsteps is a convenient means for identifying discrete activities orsteps, and unless otherwise specified, recited process steps can bearranged in any sequence. Expressing a range includes all integers andfractions thereof within the range. Expressing a minimum or up to atemperature or a temperature range in a process, or of a reactionmixture, or of a melt or applied to a melt, or of a polymer or appliedto a polymer means in all cases that the reaction conditions are set tothe specified temperature or any temperature, continuously orintermittently, within the range or above the lower stated amount orbelow the upper stated amount; and that the reaction mixture, melt orpolymer are subjected to the specified temperature as set points and itis not required that the particular reaction mixture, melt or polymeractually reach or remain at that particular temperature.

The intrinsic viscosity values described throughout this description areset forth in dL/g units as calculated from the inherent viscositymeasured at 25° C. in 60/40 wt/wt phenol/tetrachloroethane according tothe calculations immediately prior to Example 1 below.

The L* value is a measure of brightness. This value is measured inaccordance with ASTM D 1746 for discs, plaques, preforms or bottlesidewalls (transmission mode). Color measurement theory and practice arediscussed in greater detail in “Principles of Color Technology”, pp.25-66 by John Wiley & Sons, New York (1981) by Fred W. Billmeyer, Jr.Brightness is measured as L* in the CIE 1976 opponent-color scale, with100% representing a colorless sample transmitting 100% at allwavelengths. An L* of 100 in a colorless sample in the transmittancemode would be perfectly transparent, while an L* of 0 in a colorlesssample would be opaque.

When catalyzed with appropriate transition metals, such as cobalt,blends of polyesters with polyamides can scavenge oxygen, producingarticles with very low oxygen transmission rates. Addition of cobalt tosuch blends by way of a concentrate comprising at least a polyesterpolymer and the transition metal provides at least one advantage, if nota combination of several advantages, over other methods of incorporatingthe cobalt, such as liquid carrier addition or in other embodimentsadding the metal to the melt phase for the manufacture of the polyesterpolymer.

Not all embodiments will achieve all the advantages described herein.However, at least one of the advantages can be obtained in one or moreof the embodiments described herein, such advantages being:

-   -   liquid carriers can volatilize when introduced to warm (from the        drying step) polyester and/or polyamide pellets, either at the        injection molding machine, or in a separate preblending step.        Volatilization can be significantly reduced or eliminated        through the use of a solid polyester based metal concentrate;    -   the addition of the solid concentrate results in easier clean up        than addition of cobalt in a liquid carrier;    -   a solid concentrate of transition metal and polyester is more        stable than the corresponding liquid carrier containing the        transition metal. For example, cobalt in a liquid carrier may        settle resulting in concentration variation throughout the        sample of carrier. We have also noticed significant changes over        time in the flow characteristics of some liquid concentrates,        while polyester based cobalt concentrates are stable;    -   the color of preforms and bottles stretch blow molded from the        preforms containing polyamides and made with the cobalt        containing solid concentrates have better b* and L* color than        those made with cobalt contained in a liquid carrier;    -   significant flexibility in the process for making blends of        polyester, polyamide and cobalt. In particular, the concentrate        approach allows all materials, including the concentrate        pellets, polyester pellets and polyamide pellets, to be mixed        and then conveyed in conventional PET processing equipment and        dried at normal PET drying conditions. Surprisingly, this        “codrying” results in materials with better color than similar        compositions prepared using liquid concentrates where the        polyester and polyamide components are dried separately prior to        mixing;    -   by using solid concentrates containing cobalt over liquid        carriers containing cobalt, the haze level of bottle preforms is        reduced when the cobalt is obtained from a solid cobalt        concentrate relative to a comparable preform containing the same        or less amount of cobalt obtained from a liquid carrier;    -   the addition of cobalt through the use of solid concentrates is        more effective as an oxidation catalyst than cobalt which has        been added during the melt phase polymerization of the bulk        polyester polymer; and    -   highly modified polyester polymers compounded with the        transition metals are easier to pelletize because such        concentrates are not as brittle and form fewer sticks compared        to the same concentrates made with polyester polymers which are        only slightly modified.

In a first embodiment, there is provided a solid concentrate obtained bymelt compounding a transition metal compound in an amount ranging from1000 ppm to 40,000 ppm (by metal) and a polyester polymer having anIt.V. of at least 0.55 dL/g in an amount of at least 40 wt. %, eachbased on the weight of the concentrate.

In all embodiments, the pellet concentrate is a solid when measured at 1atmosphere and at 25° C. In the first embodiment, the concentratecontains a transition metal, added during melt compounding, present inan amount ranging from 1000 ppm to 40,000 based on the metal atomcontent. In one embodiment, the amount of metal is suitable to provide apreform containing from 30 ppm, or from 50 ppm up to 500 ppm, or up to300 ppm transition metal. As used throughout, a stated ppm range ofmetal, or “by metal” is based on the weight of the metal component ofthe metal compound added and not on the weight of the metal compound.Suitable amounts of metal within the concentrate range from at least1500 ppm, or at least 2000 ppm, or at least 2500 ppm. Concentrates maycontain amounts of metal within the concentration range of at least 1000ppm, or at least 2,000 ppm, or at least 3,000 ppm, and up to 40,000 ppm,or up to 20,000 ppm, or up to 15,000 ppm, or up to 10,000 ppm, or up to8000 ppm, or up to 7000, or up to 6000, or less than 5000. The amount ofmetal may be measured by X-ray fluorescence (X-Ray) or InductivelyCoupled Plasma-Mass Spectrometry (ICP).

The type of transition metal present in the concentrate is effective toactivate or promote the oxidation of an oxidizable polymer such as apolyamide polymer. The mechanism by which these transition metalsfunction to activate or promote the oxidation of the polyamide polymeris not certain. For convenience, these transition metals are referred toherein as an oxidation catalysts, but the name does not imply that themechanism by which these transition metals function is in fact catalyticor follows a catalytic cycle. The transition metal may or may not beconsumed in the oxidation reaction, or if consumed, may only be consumedtemporarily by converting back to a catalytically active state. As notedin U.S. Pat. No. 5,955,527, incorporated fully herein by reference, ameasure of the catalyst may be lost in side reactions, or the catalystmay be viewed as an initiator “generating free radicals which throughbranching chain reactions leads to the scavenging of oxygen out ofproportion to the quantity of “catalyst”.”

Suitable examples of transition metals include cobalt, copper, rhodium,platinum, rhenium, ruthenium, palladium, tungsten, osmium, cadmium,silver, tantalum, hafnium, vanadium, titanium, chromium, nickel, zinc,and manganese. Preferred is cobalt.

The use of the word “metal”, or any of the specific metals such ascobalt, means the metal in any oxidation state. Examples of cobaltinclude cobalt added to or at least a portion of which is present in the+2 or +3 oxidation state in the concentrate, or cobalt metal in the 0oxidation state as elemental cobalt. Most preferred is cobalt added inthe +2 oxidation state.

In an oxidation state other than 0, a metal is typically added orpresent as a salt, oxide, or other counter-ion. Suitable counter-ions tothe metal among others include carboxylates, such as neodecanoates,octanoates, acetates, lactates, naphthalates, malates, stearates,acetylacetonates, linoleates, oleates, palmitates, 2-ethylhexanoates, orethylene glycolates; oxides; borates; carbonates; chlorides; dioxides;hydroxides; nitrates; phosphates; sulfates; or silicates and mixturesthereof.

Concentrates containing about 2000 to 8000 ppm cobalt, with cobalt addedin +2 oxidation state in the form of a salt are preferred. Cobaltneodecanoate and cobalt acetate are examples of preferred salts. Cobaltneodecanoate is particularly preferred.

The concentrates of the first embodiment may be prepared by a variety ofmelt compounding methods known in the art. Any suitable equipmentdesigned to melt the polyester polymer pellets, to combine thecomponents of the concentrate, and mix them may be used. Alternatively,the functions may be performed in more than one piece of equipment. Thismay be in continuous or batch processes. Example of equipment that maybe used include, but are not limited to, two-roll mills, two rotormixers with open mixing chambers, internal mixers with a single rotor,internal mixers with multiple counterrotating rotors, internal mixerswith multiple corotating rotors, internal mixers with multiple mixingchambers, single screw extruders, planetary screw extruders, corotatingtwin screw extruders, counterrotating twin screw extruders conicalextruders, and the like. These mixing devices are well known in the artand described in many references, such as W. Michaeli, “PlasticsProcessing: An Introduction”, Carl Hanser Verlag, Munich, 1995; “PolymerMixing: Technology and Engineering”, J. L. White, A. Y. Coran and A.Moet, Eds., Carl Hanser Verlag, Munich, 2001; and “Plastics Compounding:Equipment and Processing”, D. B. Todd, Ed., Carl Hanser Verlag, Munich,1998.

Alternatively, the components may also be mixed using static mixers inwhich the mixing elements are stationary and the mixing is accomplishedby multiple reorientations of a melt stream containing the moltenpolymer and the cobalt salt as it flows through the static elements, ormolten polymer may be mixed with the cobalt salt in stirred vessels.

The cobalt salt may be a mixture of cobalt salts and may be fed neatinto the process for production of the concentrate, or in a suitablecarrier.

In a preferred embodiment, manufacture of a solid polyester concentratecontaining cobalt is accomplished by either dry feeding a separatestream or streams of polyester pellet base resin(s) and a separatestream of cobalt containing additive such as cobalt neodecanoate or bydry blending the polyester with the cobalt additive which may then befed together to the melt processing zone of a twin-screw compounder suchas manufactured by Werner & Pfleiderer for melt mixing at approximately450-550 F and dispersing of the cobalt into the polyester matrix. Thepolyester/cobalt melt mixture is then quenched in water and cut intocylindrical pellets for further use in downstream application. Thesolidified pellets or concentrate can be used either in its amorphousform or it can be crystallized by agitating and heating above 300° F.for an extended time.

The concentrate also comprises a solid polyester polymer in an amount ofat least 40 wt. %, or at least 50 wt. %, or at least 60 wt. %, or atleast 80 wt. %, or at least 90 wt. %, or at least 95 wt. %, or at least98 wt. % or at least 99 wt. %, based on the weight of the concentrate.In one embodiment, the concentrate is essentially free of polymers otherthan a polyester polymer.

The polyester polymers contained in the solid concentrate may be thesame as or different from bulk polyester polymer fed to the meltprocessing zone for making the article. Suitable polyester polymers arethose which are solid at 1 atmosphere and at 25° C. Preferred polyesterpolymers are those which contain aromatic repeating units, such as thosecontaining repeating units of terephthalic acid residues, isophthalicacid residues, or naphthalenic acid residues. Polyethyleneterephthalate, poly(dimethyl cyclohexane terephthalate),polytrimethylene terephthalate, polyethylene naphthalate, and copolymersthereof modified with up to 60 mole % of a modifier are preferred.

Suitable polyethylene terephthalate homopolymers and copolymers aremodified with one or more polycarboxylic acid modifiers in a cumulativeamount of 40 mole % or less, or 25 mole % or less, or 15 mole % or less,or mole % or less, or 8 mole % or less, and/or one or more hydroxylcompound modifiers in an amount of 60 mol % or less, or 50 mole % orless, or 15 mole % or less, or 10 mole % or less, or 8 mole % or less(collectively referred to for brevity as “PET”) and polyethylenenaphthalate homopolymers and copolymers modified with a cumulativeamount of 40 mole % or less, or less than 15 mole %, or 10 mole % orless, or 8 mole % or less, of one or more polycarboxylic acid modifiersor modified less than 60 mol %, or less than 50 mole %, or less than 15mole %, or 10 mole % or less, or 8 mole % or less of one or morehydroxyl compound modifiers (collectively referred to herein as “PEN”),and blends of PET and PEN. A modifier polycarboxylic acid compound is acompound other than an acid compound present in an amount of greaterthan 50 mole %. A modifier h hydroxyl compound is a compound other thanethylene glycol.

The preferred polyester polymer is polyalkylene terephthalate, and mostpreferred is PET.

In a second embodiment, there is provided a polyester polymerconcentrate comprising at least 1000 ppm of a transition metal, andpolyester polymers in an amount of least 40 wt. %, each based on theweight of the concentrate, wherein at least a portion of the polyesterpolymers comprise highly modified polyester polymers containing hydroxylmodifier residues in an amount ranging from 20 mole % to 60 mole %,based on the all the moles of hydroxyl compound residues present in thepolyester polymer and/or polycarboxylic acid modifiers in an amountranging from 20 mole % to 60 mole %, based on all the moles ofpolycarboxylic acid residues present in the polyester polymer.Desirably, the amount of highly modified polyester polymers is at least25 wt. %, or at least 50 wt. %, or at least 75 wt. %, or at least 80 wt.%, or at least 90 wt. %, or at least 95 wt. %, or up to 100 wt. %, ofthe total amount of polyester polymers present in the concentrate. Thetechnique for manufacturing the concentrate in this second embodiment isnot particularly limited.

The metal content in the second embodiment is not particularly limited.Preferably, the transition metal concentration content in the secondembodiment is preferably at least 1000 ppm, or at least 2,000 ppm, or atleast 3,000 ppm, and up to 40,000 ppm, or up to 20,000 ppm, or up to15,000 ppm, or up to 10,000 ppm, or up to 8000 ppm, or up to 7000, or upto 6000, or less than 5000.

At least a portion of the polyester polymers used in the concentrate ofthis second embodiment contain are copolymerized with a polycarboxylicacid or hydroxyl modifier, more preferably a hydroxyl modifier, suchthat the polymer contains the residues of the modifier used in an amountof at least 20 mole %, or at least 25 mole %, or at least 30 mole %, andup to 60 mole %, based on the moles of corresponding polycarboxylic acidresidues or hydroxyl compound residues present in the polymer.Desirably, the modifier and especially the hydroxyl modifier iscopolymerized in an amount ranging from 25 mole % to 60 mole %, or 25mole % to 50 mole %, or 30 mole % to 50 mole %, based on thecorresponding residues present in the polymer.

We have found that highly modified polyester polymers compounded withthe transition metals are easier to pelletize because such blends arenot as brittle compared to the same blends made with polyester polymerswhich are only slightly modified. Fewer “sticks” are formed duringextrusion and cutting. A “stick” is a rod which forms as a result ofstrands breaking at the cutter blades. Sticks are characterized as rodshaped instead of pellet shaped, often exceeding a length of ⅛″. Suchsticks are undesirable when fed at the throat of an injection moldingmachine.

Since the highly modified polymers are less brittle when compounded withtransition metals, higher loadings of transition metal into thepolyester polymer are also now possible. Further, by using highlymodified polyester polymers, the processing temperature of the melt inan extruder can lowered.

In this second embodiment, the transition metal may be added into themelt phase process for making the polyester polymer or may be added bymelt compounding with a polyester polymer. However, it is preferred toadd the transition metal by melt compounding the highly modifiedpolyester polymer with the transition metal to obtain more advantages asnoted above with respect to melt compounding.

More particularly, in this embodiment and preferably in otherembodiments as described herein, the preferred polyester polymer used inthe concentrate comprises:

-   -   (i) a polycarboxylic acid component comprising at least 60 mole        %, or at least 85 mole %, or at least 92 mole %, or at least 94        mole %, residues of terephthalic acid, derivates of terephthalic        acid, naphthalene-2,6-dicarboxylic acid, derivatives of        naphthalene-2,6-dicarboxylic acid, or mixtures thereof, and    -   (ii) a hydroxyl component comprising at least 40 mole %, or at        least 50 mole %, and up to 80 mole % residues of ethylene        glycol, with at least 20 mole %, or at least 25 mole %, or at        least 30 mole %, and up to 60 mole %, of residues of a hydroxyl        modifier based on 100 mole percent of the polycarboxylic acid        residues and 100 mole percent hydroxyl residues in the polyester        polymer.

The reaction of a polycarboxylic acid compound with a hydroxyl compoundduring the preparation of the polyester polymer is not restricted to thestated mole % ratios since one may utilize a large excess of a hydroxylcompound if desired, e.g. on the order of up to 200 mole % relative tothe 100 mole % of polycarboxylic acid used. The polyester polymer madeby the reaction does, however, contain the stated amounts of aromaticdicarboxylic acid residues and hydroxyl residues. Derivates ofterephthalic acid and naphthalane dicarboxylic acid include C₁-C₄dialkylterephthalates and C₁-C₄ dialkylnaphthalates, such asdimethylterephthalate and dimethylnaphthalate

In addition to a diacid component of terephthalic acid, derivates ofterephthalic acid, naphthalene-2,6-dicarboxylic acid, derivatives ofnaphthalene-2,6-dicarboxylic acid, or mixtures thereof, thepolycarboxylic acid component(s) of the present polyester may includeone or more additional modifier polycarboxylic acids. Such additionalmodifier polycarboxylic acids include aromatic dicarboxylic acidspreferably having 8 to 14 carbon atoms, aliphatic dicarboxylic acidspreferably having 4 to 12 carbon atoms, or cycloaliphatic dicarboxylicacids preferably having 8 to 12 carbon atoms. Examples of modifierdicarboxylic acids useful as an acid component(s) are phthalic acid,isophthalic acid, cyclohexanedicarboxylic acid, cyclohexanediaceticacid, diphenyl-4,4′-dicarboxylic acid, succinic acid, glutaric acid,adipic acid, azelaic acid, sebacic acid, and the like, with isophthalicacid, naphthalene-2,6-dicarboxylic acid, and cyclohexanedicarboxylicacid being most preferable. It should be understood that use of thecorresponding acid anhydrides, esters, and acid chlorides of these acidsis included in the term “polycarboxylic acid”. It is also possible fortrifunctional and higher order polycarboxylic acids to modify thepolyester.

The hydroxyl component is made from hydroxyl compounds, which arecompounds containing 2 or more hydroxyl groups capable of reacting witha carboxylic acid group. Preferred hydroxyl compounds contain 2 or 3hydroxyl groups, more preferably 2 hydroxyl groups, and preferably areC₂-C₄ alkane diols, such as ethylene glycol, propane diol, and butanediol, among which ethylene glycol is most preferred for containerapplications.

In addition to these diols, other modifier hydroxyl compoundcomponent(s) may include diols such as cycloaliphatic diols preferablyhaving 6 to 20 carbon atoms and/or aliphatic diols preferably having 3to 20 carbon atoms. Examples of such diols include diethylene glycol;propane-1,3-diol and butane-1,4-diol (each of which are consideredmodifier hydroxyl compounds if ethylene glycol residues are present inthe polymer in an amount of greater than 50 mole % based on the moles ofall hydroxyl compound residues); triethylene glycol;1,4-cyclohexanedimethanol; pentane-1,5-diol; hexane-1,6-diol;3-methylpentanediol-(2,4); neopentyl glycol; 2-methylpentanediol-(1,4);2,2,4-trimethylpentane-diol-(1,3); 2,5-ethylhexanediol-(1,3);2,2-diethyl propane-diol-(1,3); hexanediol-(1,3);1,4-di-(hydroxyethoxy)-benzene; 2,2-bis-(4-hydroxycyclohexyl)-propane;2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane;2,2-bis-(3-hydroxyethoxyphenyl)-propane; and2,2-bis-(4-hydroxypropoxyphenyl)-propane. Typically, polyesters such aspolyethylene terephthalate are made by reacting a glycol with adicarboxylic acid as the free acid or its dimethyl ester to produce anester monomer and/or oligomers, which are then polycondensed to producethe polyester.

Preferred modifiers include isophthalic acid, naphthalenic dicarboxylicacid, trimellitic anhydride, pyromellitic dianhydride, butanediol,1,4-cyclohexane dimethanol,2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, trimethylene glycol,neopentyl glycol, and diethylene glycol.

The amount of the polyester polymer in the formulated polyester polymercomposition ranges from greater than 50.0 wt. %, or from 80.0 wt. %, orfrom 90.0 wt. %, or from 95.0 wt. %, or from 96.0 wt. %, or from 97 wt.%, and up to about 99.90 wt. %, based on the combined weight of allpolyester polymers and all other polymers. The formulated polyesterpolymer compositions may also include blends of formulated polyesterpolymer compositions with other thermoplastic polymers such aspolycarbonate. It is preferred that the polyester composition shouldcomprise a majority of the formulated polyester polymer composition ofthe inventions, more preferably in an amount of at least 80 wt. %, or atleast 90 wt. %, based on the weight of the composition (excludingfillers, inorganic compounds or particles, fibers, impact modifiers, orother polymers serve as impact modifiers or which form a discontinuousphase such as may be found in cold storage food trays).

The polyester polymers can be prepared by polymerization proceduresknown in the art sufficient to effect esterification andpolycondensation. Polyester melt phase manufacturing processes includedirect condensation of a dicarboxylic acid with the diol, optionally inthe presence of esterification catalysts, in the esterification zone,followed by polycondensation in the prepolymer and finishing zones inthe presence of a polycondensation catalyst; or ester exchange usuallyin the presence of a transesterification catalyst in the ester exchangezone, followed by prepolymerization and finishing in the presence of apolycondensation catalyst, and each may optionally be solid statedaccording to known methods.

In one embodiment, the It.V. of the concentrates made with highlymodified polyester polymers ranges from about at least 0.60, or at least0.70, or at least 0.75, and up to about 1.15 dL/g.

In another embodiment, the It.V. of the polyester polymers used to makethe concentrate in a melt compounding process, and prior to preparationof the concentrate, ranges from about at least 0.55, or at least 0.65,or at least 0.70, or at least 0.75, and up to about 1.15 dL/g. In thisembodiment, the concentrates are made by melt compounding the elementstogether.

The molten polymer from the melt phase polymerization may be allowed tosolidify and/or obtain any degree of crystallinity from the melt.Alternatively, the molten polymer can be first solidified and thencrystallized from the glass.

In yet another embodiment, the polyester polymers used to make theconcentrate in a melt compounding process, or the concentratesthemselves made with highly modified polyester polymers regardless oftheir method of preparation, preferably have an It.V. of at least 0.68dL/g, or at least 0.70 dL/g, or at least 0.72 dL/g, or at least 0.76dL/g, and even at least 0.80 dL/g, such It.V. obtained in the melt phasefor the manufacture of the polyester polymer. In other words, the It.V.of the polyester polymer to which is blended the metal is obtainedwithout solid state polymerizing the polymer. Providing a polyesterpolymer with high It.V. obtained in the melt phase polycondensationreaction avoids the expensive and time consuming step of solid statepolymerizing the polymer to increase its It.V.

The polyester polymers in the concentrate may be either semicrystallineor essentially amorphous in nature. However, if the resulting polyesteris essentially amorphous (5% crystallinity or less), compositions havinga DSC Tg of about 70° C. or greater are preferred.

The polyester polymer composition used as the bulk polyester polymer fedto the melt processing zone also has a composition within the scope ofthe foregoing description. The composition of the polyester polymer inthe concentrate can be tailored through incorporation of comonomers suchas 1,4 cyclohexanedimethanol, isophthalic acid, naphthalene dicarboxylicacid, diethylene glycol, and other modifiers to adjust properties of thefinal polyester blend such as Tg and crystallization kinetics, or asneeded to match the composition of the bulk polyester polymer fed to themelt processing zone for making the article.

The composition of the article is not particularly limited. Examples ofcompositions are those in which a metal is effective to enhance thereheat rate of preforms and trays, reduce the coefficient of friction ofbottles, impact modify, and scavenge oxygen, relative to the samecompositions which do not contain the metal. For example, there isprovided an article comprising an oxidizable polymer or oxygenscavenging polymer in an amount ranging from about 1 to about 10%, orfrom 1 to 5 wt. %, from about 30 to 300 ppm, or 50 to 200 ppm, of atransition metal such as Co, and a polyester polymer present in anamount ranging from about 90 wt. % to 99 wt. % based on the weight ofall ingredients contained in the article. In such compositions, at leasta portion of the total amount of transition metal present in the articleis added to a melt processing zone by way of a solid concentratecontaining the metal. In an oxygen scavenging composition, the articlealso preferably contains zinc in an amount ranging from 50 ppm to 300ppm, preferably from 50 ppm to 150 ppm.

In all cases, the concentrate will contain a higher concentration of themetal than present in the article composition. Let down ratios of themetal concentration in the concentrate to the metal concentration in thearticle composition can range from 30:1 up to 200:1.

Any conventional process used to add concentrates to a bulk stream ofpolymer in a melt processing zone for making the article is suitable.For example, pellets of polyester, scavenger and polyester based cobaltconcentrate can be blended, either prior to or after drying, and fed toan injection molding machine or extruder, followed by melt blending andforming into an article such as a preform. Alternatively, the pelletsmay be fed to the melt processing zone as individual streams, or in acombination of streams with one or more of the streams being acombination of two or more types of pellets.

An article which is effective to scavenge oxygen contains an oxidizablepolymer in addition to the polyester polymer. Oxidizable polymersinclude polymers having an active methylene group, such as may be foundon allylic group hydrogen atoms, benzylic group hydrogens, and alphaoxyalkylene hydrogens. Such hydrogen atoms may be expressed in thefollowing respective structural moieties or repeating units as beinglinked to the carbons illustrated in bold:

wherein R is a hydrogen or an alkyl group.

Examples of oxidizable polymers include polyamide polymers, andcopolymers of α-olefins such as 1,4-butadiene with a polyester polymer.Most preferred are oxidizable polyamide polymers, especially thosecontaining a benzylic hydrogen. From a viewpoint of their commercialavailability, cost, and performance, preferred polyamides are obtainedfrom a reactant containing a xylylene moiety, or a m-xylylene moiety, ora polymer containing any one of these residues in the polymer chain.More preferred examples include poly(m-xylylene adipamide) modified orunmodified polyamides, and poly(m-xylylene adipamide-co-isophthalamide)modified or unmodified polyamides. The polyamide polymer has a numberaverage molecular weight Mn of 45,000 or less, or 35,000 or less, or25,000 or less, or 15,000 or less, or 12,000 or less, or 8,000 or less,or 5,500 or less and greater than 1,000, or greater than 3,500. Whilesuch low molecular weight polyamide polymers are not considered to be offilm forming molecular weight, their low molecular weight increases theterminal amino group concentration relative to using higher molecularweight polyamide polymers.

The concentrate of the invention is preferably substantially free of apolyamide polymer. In an oxygen scavenging composition, we have foundthat articles made from bulk polyester polymers fed to a melt processingzone along with a single stream of concentrate pellets made by meltblending a polyamide polymer, a polyester polymer, and a metal such ascobalt surprisingly do not scavenge oxygen as effectively as those madeby feeding bulk polyester polymer pellets to a melt processing zonealong with two other distinct streams of pellets, one comprisingconcentrates made by melt blending a polyester polymer with the metaland another stream comprising polyamide polymer pellets. Accordingly,the concentrate particles of the invention are preferably substantiallyfree of (e.g. less than 0.5 wt. %), and more preferably does not containany added polyamide polymer.

The polyester polymer particles, the concentrate particles, and thepolyamide polymer particles may be fed to the melt processing zone asindividual streams or as combined streams of particle/particle dryblends. In this preferred embodiment, the polyamide polymers are notmelt blended with the polyester polymers in the concentrates.Preferably, the oxygen scavenging polymer is fed to a melt processingzone as a distinct separate stream from the concentrate particles.

Thus, in another embodiment, there is provided a process for themanufacture of a preform comprising combining solid polyester particlescomprising polyester polymers, solid polyamide particles comprisingpolyamide polymers, and solid concentrate particles obtained by meltcompounding together a polyester polymer in an amount of at least 40 wt.% and a transition metal in an amount ranging from 1000 ppm to 40,000ppm, based on the weight of the solid concentrate particles, into anmelt processing zone, forming a melt, and forming an article directlyfrom the melt. In this embodiment, it is more preferred that the solidconcentrate is substantially free of a polyamide polymer.

The polyester polymer and metal are separately, or in combination,optionally dried in an atmosphere of dried air or dried nitrogen. In onemethod of incorporation, the polyester polymer particles and the metalare melt compounded, for example, in a single or twin screw extruder.After completion of the melt compounding, the extrudate is withdrawn instrand form, and recovered according to the usual way such as cutting.By using a highly modified polyester polymer, the strands are lessbrittle when drawn through the water bath prior to cutting, resulting infewer strands shattering and fewer sticks, and providing the benefitthat higher loadings of transition metal are now possible.

One the transition metal concentrate pellets are made, they are fed intoa melt extrusion zone for making the article. A separate stream ofpolyester polymer particles, a third stream containing a source ofpolyamide polymer, and optionally a fourth stream containing otheradditives such as colorant, acetaldehyde scavengers, reheat agents, UVabsorbers or inhibitors, stabilizers, thermal stabilizers, etc., are fedto a melt processing zone for making the article, and the concentrate islet down into the melt processing zone in an amount to provide thedesired level of metal in the finished article.

In yet another embodiment a blend comprising solid polyester particlescomprising polyester polymers, solid polyamide particles comprisingpolyamide polymers, and a solid concentrate comprising a polyesterpolymer and a transition metal present in an amount ranging from 1000ppm to about 40,000 ppm are simultaneously dried in a drying zone, underconditions effective to at least partially remove moisture from theblend. In this embodiment, the method for making the concentrate is notparticularly limited, and the types of polyester polymers used and theirmolecular weight as determined by It.V. are also not limited. Themoisture level of the blend of particles can be reduced down to lessthan 0.015 wt. %, or less than 0.010 wt. %, or less than 0.005 wt. %. Inan apparatus containing a drying zone, radiant or convective heat, orelectromagnetic or microwave radiation, or any other source for removalof moisture, is emitted from a drying zone or is passed through at leasta portion of the mechanical drying zone and contacts the particle blendto remove at least a portion of surface and/or internal water moisture.Surprisingly, this co-drying method eliminates the need for multipledryers and results in better color (higher L*, lower, b*, lower Yl) thanwhen the polyamide and polyester are dried separately and cobalt isadded via a liquid concentrate.

In another embodiment, the preforms obtained using concentrates havelower haze than those obtained by using cobalt in a liquid carrier atcomparable levels of cobalt. The haze levels of bottle sidewalls madefrom preforms containing 150 ppm or less of cobalt using theconcentrates is preferably 4.0% or less, or 3.5% or less.

The articles obtained by the concentrates of the invention may beextruded products such as sheets and fibers, or injection moldedarticles such as bottle preforms and other shapes. In a preferredembodiment, the articles produced from the melt processing zone are thepreforms, sheets, and trays for packaging food, pharmaceuticals, medicalsupplies, and beverages.

The articles are obtained directly from the melt in the melt processingzone for forming the articles. By directly is meant that the meltpresent in the melt processing zone for making the article is notpelletized and then remelted at later date to form the article.

The following non-limited examples further illustrate variousembodiments of the invention.

EXAMPLES Oxygen Transmission Rate (OTR) Procedure

The oxygen transmission rate test is performed using stretch blow moldedbottles. The bottles are fitted following blow molding for oxygenpackage transmission testing. Prior to measurement, the bottle is sealedby gluing it to a brass plate that is connected to a 4 way valve overthe finish. This mounting technique seals the bottle, while allowing forcontrol of test gas access. The mounting is assembled as follows. Firsta brass plate is prepared by drilling two ⅛ inch holes into the plate.Two lengths of ⅛ soft copper tubing (which will be designated A and B)are passed through the holes in the plate and the gaps between the holesand the tubes are sealed with epoxy glue. One end of each of these tubesis attached to the appropriate ports on a 4-way ball valve (such asWhitey model B-43YF2). Tubing (which will be designated C and D) andconnections are also attached to the other ports of the ball valve toallow the finished assembly to be connected to an Oxtran oxygenpermeability tester (Modern Control, Inc. Minneapolis, Minn.).

This mounting is then glued to the finish of the bottle to be tested sothat tubes A and B extend into the interior of the bottle. The open endof one tube is positioned near the top of the package and the open endof the other is positioned near the bottom to ensure good circulation ofthe test gas within the bottle. Gluing is typically performed in twosteps using a quick setting epoxy to make the initial seal andtemporarily hold the assembly together and then a second coating of amore rugged Metalset epoxy is applied. If desired the brass plate may besanded before mounting to clean the surface and improve adhesion. If the4 tubes are correctly connected to the 4-way valve, then when the valveis in the “Bypass” position, tubes A and B communicate and tubes C and Dcommunicate, but tubes A and B do not communicate with tubes C and D.Thus the package is sealed. Similarly, when the valve is in its “Insert”position, tubes A and D communicate and tubes B and C communicate, but Aand D do not communicate with tubes B and C, except through the interiorof the bottle. Thus the bottle can be swept with purge or test gas.

Once the bottle is mounted on the assembly, it is swept with anoxygen-free gas, and the conditioning period begins. After severalminutes of purging, the 4-way valve is moved to the Bypass position,sealing the bottle. At that point the entire bottle and mountingassembly may be disconnected from the purge gas supply withoutintroducing oxygen into the interior of the bottle. Typically 2 or 3bottles of each formulation are mounted for testing.

When the oxygen transmission rate of the bottle is to be tested, it isplaced inside an environmental chamber. Under normal operation thesechambers control the external conditions at 23° C. plus or minus 1° C.and 50% relative humidity plus or minus 10%. These chambers containtubing connections to an Oxtran 1050 or Oxtran 1050A instrument and themounting is connected to the Oxtran tester via tubes C and D. Carriergas (nitrogen containing on the order of 1% hydrogen), which ishumidified using a bubbler, is supplied to the instruments and thetubing in the environmental chamber. Both the Oxtran 1050 and 1050A usea coulometric sensor to measure oxygen transmission rates and both havepositions for 10 samples to be mounted on the instrument at one time.Typically, 9 test bottles and 1 control package were run in a set. Oncesamples were mounted in the chamber, the 4-way valve is turned to theInsert position and the system is allowed to recover from theperturbation caused by this process.

After allowing the system to recover, the test is then begun by“inserting” the instrument sensor in-line. The test sequence iscontrolled by a specially written LabView™ software interface for theinstrument. Basically, the instrument automatically advances through thetest cells using a preset interval that allows the instrument tostabilize after each cell change as the test gas from the bottle mountedon the cell is routed through the coulometric sensor, generating acurrent. That current is passed through a resistor, which creates avoltage that is proportional to the oxygen transmission rate of thepackage plus the leak rate of that cell and package assembly. Typicallythe instrument is allowed to index through each of the cells 3 or moretimes and the average of the last 3 measurements is used. Once thesereadings are obtained, the 4-way valves are moved to their Bypasspositions and this process is repeated, providing a measure of the leakrate for the cell and assembly. This value is subtracted from the valueobtained for the package, cell and assembly to yield the value for thepackage. This value is corrected for the average barometric pressure inthe laboratory and reported as the oxygen transmission rate (OTR) of thebottle (in either cc(STP) of oxygen/day or μl (STP) of oxygen/day). Atthis point the test is terminated and the bottles are removed from theinstrument (with the 4-way valves still in the Bypass position).

Between tests, bottles are stored at ambient (RH, lighting, barometricpressure) conditions in a lab (22° C. plus or minus 4° C.) with theinterior isolated from air. After a period of time, the bottle isreconnected to the Oxtran and a new set of transmission measurementscollected. In this manner, it is possible to monitor the behavior of thebottle over several weeks or months.

The following cobalt concentrates were used in the examples

-   -   Solid Concentrate 1: is a polyester based concentrate of cobalt        neodecanoate (TEN-CEM™ 22.5%) in Polyester Polymer Resin 3. The        concentrate can be made by mixing the cobalt salt into Resin 3        melt using a 30 mm Werner & Pfleiderer twin screw extruder. The        approximate level of cobalt in the concentrate is 3400 to 3900        ppm. Concentrate 1 is the concentrate for Examples 1, 2, 3, 6, 7        and 8.    -   Solid Concentrate 2 is a polyester based concentrate of cobalt        acetate in Polyester Polymer Resin 4 produced by mixing the        cobalt salt into a PET melt using a 30 mm Werner & Pfleiderer        twin screw extruder. The approximate level of cobalt in the        concentrate is 3400 to 3900 ppm.    -   Liquid Concentrate 1 is a concentrate of cobalt neodecanoate in        a liquid dispersion with approximately 63,000 to 68,000 ppm        cobalt.    -   Liquid Concentrate 2 is concentrate of cobalt neodecanoate in a        liquid dispersion with approximately 35,000 to 40,000 ppm        cobalt.    -   PA-A: is a poly(m-xyxlenediamine adipamide) commercially        available from Mitsubishi Gas Chemical America, Inc., New York,        N.Y. as MXD-6 grade 6007.    -   PA-B: is a poly(m-xyxlenediamine adipamide) commercially        available from Mitsubishi Gas Chemical America, Inc., New York,        N.Y. as MXD-6 grade 6121.    -   Polyester Polymer Resin 1: About a 0.87 intrinsic viscosity        (It.V.) solid stated polyester polymer composition containing        residues of dimethyl terephthalate, ethylene glycol, and        cyclohexane dimethanol, with cyclohexane dimethanol residues        representing about 1.8 mol % of the glycol residues, containing        Ti, Mn, and Sb metal residues, phosphorus, iron, and UV dye and        red and blue toners.    -   Polyester Polymer Resin 2: About a 0.80 ItV solid stated        polyester polymer composition containing residues of        terephthalate acid, ethylene glycol, and cyclohexane dimethanol,        with cyclohexane dimethanol residues representing about 1.5 mole        % of the glycol residues and red and blue toners and with Sb as        a catalyst and phosphorus.    -   Polyester Polymer Resin 3: About a 0.80 ItV solid stated        polyester polymer composition containing residues of dimethyl        terephthalate, ethylene glycol, and cyclohexane dimethanol, with        cyclohexane dimethanol residues representing about 3.5 mol % of        the glycol residues, with red and blue toners and Ti, Mn and Sb        catalyst residues along with phosphorus.    -   Polyester Polymer Resin 4: About a 0.76 ItV solid stated        polyester polymer composition containing residues of dimethyl        terephthalate, ethylene glycol and cyclohexane dimethanol with        cyclohexane dimethanol residues representing about 1.8 mole % of        the glycol residues, Sb, phosphorus, and Zn catalyst residues,        along with red and blue toners.    -   Polyester Polymer Resin 5: About a 0.78 It.V. solid stated        polyester polymer composition containing residues of dimethyl        terephthalate and ethylene glycol, cyclohexane dimethanol, with        cyclohexane dimethanol residues representing about 1.8 mol % of        the glycol residues with Zn and Sb catalyst residues,        phosphorous, Fe, along with UV dye and red and blue toners.    -   Polyester Polymer Resin 6: a 0.81 It.V. solid stated polyester        polymer composition containing residues of dimethyl        terephthalate and ethylene glycol, cyclohexane dimethanol, with        cyclohexane dimethanol residues representing about 1.8 mol % of        the glycol residues, with Zn and Sb catalyst residues,        phosphorous, Fe, and UV dye and red and blue toners    -   Polyester Polymer Resin 7: a 0.82 It.V. solid stated polyester        polymer composition containing residues of dimethyl        terephthalate and ethylene glycol, cyclohexane dimethanol, with        cyclohexane dimethanol residues representing about 1.8 mol % of        the glycol residues, with Zn and Sb catalyst residues,        phosphorous, Fe, and UV dye and red and blue toners.    -   Polyester Polymer Resin 8: a 0.78 ItV solid stated polyester        polymer composition containing residues of dimethyl        terephthalate and ethylene glycol, Sb catalyst residue,        phosphorous, Zn catalyst residue, and cobalt in an amount of 55        to 65 ppm.    -   Polyester Polymer Resin 9: a 0.71 ItV solid stated polyester        polymer composition containing residues of dimethyl        terephthalate, ethylene glycol and dimethyl isophthalate with        dimethyl isophthalate residues representing about 2 mole % of        the acid residues, Sb, phosphorous, Zn, and cobalt in an amount        of 60 to 90 ppm.    -   Polyester Polymer Resin 10: is a 0.76 ItV solid stated polyester        polymer composition containing residues of dimethyl        terephthalate, ethylene glycol and dimethyl isophthalate with        dimethyl isophthalate residues representing about 2 mole % of        the acid residues, Sb, phosphorous, Zn, and cobalt in an amount        of 60 to 70 ppm.    -   Polyester Polymer Resin 11: a 0.81 ItV solid stated polyester        polymer composition containing residues of dimethyl        terephthalate, ethylene glycol and dimethyl isophthalate with        dimethyl isophthalate residues representing about 1.9 mole % of        the acid residues, Sb, phosphorous, Mn, Ti, and cobalt in an        amount of 100 to 110 ppm.    -   Polyester Polymer Resin 12: About a 0.76 ItV solid stated        polyester polymer composition containing residues of        terephthalic acid, ethylene glycol and cyclohexane dimethanol        with cyclohexane dimethanol residues representing about 1.8 mole        % of the glycol residues, Sb, phosphorous, and red and blue        toners.    -   Polyester Polymer Resin 13: About a 0.80 ItV solid stated        polyester polymer composition containing residues of dimethyl        terephthalate, ethylene glycol, and cyclohexane dimethanol, with        cyclohexane dimethanol residues representing about 4.5 mol % of        the glycol residues, with red and blue toners and Zn and Sb        catalyst residues along with phosphorus.    -   Polyester Polymer Resin 14. About a 0.80 ItV polyester polymer        composition containing residues of dimethyl terephthalate,        ethylene glycol, and cyclohexane dimethanol, with cyclohexane        dimethanol residues representing about 31 mol % of the glycol        residues, with red and blue toners and Ti and Mn catalyst        residues along with phosphorus. The It.V. of this resin is        obtained in a melt phase polymerization and is not solid state        polymerized.    -   Polyester Polymer Resin 15. About a 0.80 ItV polyester polymer        composition containing residues of dimethyl terephthalate,        ethylene glycol, and cyclohexane dimethanol, with cyclohexane        dimethanol residues representing about 31 mol % of the glycol        residues, with red and blue toners and Ti and Mn catalyst        residues along with phosphorus. The It.V. of this resin is        obtained in a melt phase polymerization and is not solid state        polymerized

The glycol portion of each of the PET resins also contains low levels(less than 5 mol %) DEG residues, which are present as a naturalbyproduct of the melt polymerization process and may also beintentionally added as a modifier.

Example 1

This example demonstrates that it is preferred to let down theconcentrate free of added polyamide polymer into an injection moldingmachine. 25 gram preforms and 20 oz straightwall bottles were producedfrom the following (nominal) oxygen scavenging compositions set forth inTable 1. Cobalt Method of addition PA-A content amt to Melt ProcessingZone Sample # (wt %) (ppm) PA-A Cobalt 1 0 0 NA NA 2 3 0 Neat PA-Apellets NA 3 3 150 PA-A/Cobalt Concentrate 4 3 150 Neat PA-A pelletsSolid Concentrate 1 5 3 70 Neat PA-A pellets Solid Concentrate 1 6 2 100PA-A/Cobalt Concentrate

The bulk polyester polymer pellets fed to the injection molding machineis Polyester Polymer Resin 1. The concentrate used in the preparation ofsamples 3 and 6 is a polyester based concentrate of cobalt neodecanoate(TEN-CEM 22.5%) and PA-A in Polyester Polymer Resin 3. The concentratecan be made by mixing the cobalt salt and PA-A into Resin 3 using a 30mm Werner & Pfleiderer twin screw extruder. The approximate level ofcobalt in the concentrate is about 2000 ppm and the approximate level ofPA-A in the concentrate is 40%. The components of this concentrate weredried prior to its preparation. The cobalt neodecanoate was driedovernight at 40° C. under vacuum, Polyester Polymer Resin 3 was driedwith dehumidified air for 6 hrs at 325° F., and the PA-A was dried withdehumidified air for 6 hrs at 150° F.

The preforms are made by introducing the bulk Polyester Polymer Resin 1pellets and the sources of cobalt and/or PA-A by the following method:

The PA-A and the PA-A/Co Concentrate were dried at 150 F while the bulkPET resin was dried in a separate system at 325 F. Solid Concentrate 1was not dried. After drying but before injection molding, the PA-A orPA-A/Co Concentrate, bulk PET, and Solid Concentrate 1 were physicallyblended using a ribbon mixer. The blend was fed into a drying hopperwith a temperature set point of 325 F, located directly over the feedthroat of the injection molding machine. Extruder and manifoldtemperatures were set at 275° C. Clear preforms were molded using aHusky LX160PET-P60/50-E42 and an 8 cavity, 25 gram preform mold with a28 mm finish.

Straight wall, 20 oz., carbonated soft drink style containers were blowmolded using a Sidel SBO 2/3 at an output rate of 1200bottles/hour/mold. A water temperature setting of 50 F was used to chillthe blow mold cavities. Blow mold processing conditions were adjusted toproduce containers with equivalent distribution of material throughoutthe bottle for each Sample to be submitted for OTR testing. Materialdistribution was characterized by dividing the container into sectionsand weighing each section. Material distribution was also characterizedby measuring the thickness of the container wall using a Hall effectsensor by Magna-Mike Model 8000. Oven power was the primary adjustmentmade to achieve equivalent material distribution for each Sample. Ovenprofile configuration and pre-blow timing were also adjusted in someinstances.

2 bottles per set were mounted and purged with oxygen free gas about 2days after blowing and the OTR's of these samples were testedperiodically. Results of these tests are presented in Table 2. FIG. 1 isa graphical illustration of the data presented in Table 2. As can beseen from the graph, the OTR of bottles made by letting down the streamof solid concentrate pellets of melt blended polyester polymers andcobalt, and a separate distinct stream of PA-A polyamide polymer pelletswas lower and the induction period shorter than bottles made with astream of concentrate melt blended pellets of PA-A polyamide polymer,polyester polymer, and metal. TABLE 2 Days Sample 1 Sample 2 Sample 3Sample 4 Sample 5 Sample 6 since OTR OTR OTR OTR OTR OTR blowing(cc/day) bottle # (cc/day) bottle # (cc/day) bottle # (cc/day) bottle #(cc/day) bottle # (cc/day) bottle # 9 0.0559 2 0.0382 2 0.0367 2 0.01932 0.0364 2 0.0405 2 10 0.0571 1 0.0395 1 — — 0.0280 1 0.0379 1 13 0.05591 — — 0.0386 1 — — 0.0388 1 20 — — 0.0271 1 0.0383 2 0.0007 2 0.0286 246 0.0558 1 0.0360 1 0.0340 2 0.0006 2 0.0008 1 0.0342 1 49 0.0543 10.0374 2 0.0303 1 0.0008 1 −0.0036 2 0.0339 2 55 0.0523 1 0.0361 10.0320 2 0.0009 2 0.0007 1 0.0340 1 80 0.0515 2 — — 0.0268 2 0.0019 10.0009 1 0.0289 2 83 0.0525 1 0.0340 1 0.0239 1 0.0008 2 0.0012 2 0.02621 83 0.0501 2 0.0346 2 — — — — 0.0011 1 109 — — 0.0373 3 0.0277 1 0.00042 — — 0.0301 2 109 — — — — — — 0.0008 1 — — 0.0300 1 158 0.0533 1 0.02771 0.0174 2 0.0010 1 0.0014 2 0.0223 2 158 0.0564 2 0.0327 2 0.0191 10.0007 2 0.0019 1 0.0222 1

Example 2

This example demonstrates that concentrates are effective at catalyzingoxygen scavenging activity over a range of compositions.

25 gram preforms and 20 oz straightwall bottles were produced from thefollowing (nominal) oxygen scavenging compositions set forth in Table 3.TABLE 3 PA target Co amount Sample # Bulk PET amt (wt %) PA Type (ppm) 7Resin 2 1 PA-A 100 8 Resin 2 3 PA-A 100 9 Resin 2 5 PA-A 100 10 Resin 23 PA-B 30 11 Resin 2 3 PA-B 150 12 Resin 2 5 PA-B 30 13 Resin 2 5 PA-B150 14 Resin 1 3 PA-A 100

In Samples 7-14, the source of cobalt was Solid Concentrate 1. Theamount of cobalt added to the melt processing zone in the injectionmolding machine is varied to yield the stated amounts of cobalt in thearticle. The stream of bulk polyester polymer particles is as set forthin the second column of Table 3. The PA was fed to the injection moldingmachine as a separate stream of polyamide pellets.

The preforms and bottles are prepared by the following method:

Both types of PA were dried at 150 F while the bulk PET resin was driedin a separate system at 325 F. Solid Concentrate 1 was not dried. Afterdryng but before injection molding, the selected PA, bulk PET, and SolidConcentrate 1 were physically blended using a ribbon mixer. The blendwas fed into a drying hopper with a temperature set point of 325 F,located directly over the feed throat of the injection molding machine.Extruder and manifold temperatures were set at 536 F. Clear preformswere molded using a Husky LX160PET-P60/50-E42 and an 8 cavity, 25 gramperform mold with a 28 mm finish.

Straight wall, 20 oz., carbonated soft drink style containers were blowmolded using a Sidel SBO 2/3 at an output rate of 1200bottles/hour/mold. A water temperature setting of 50 F was used to chillthe blow mold cavities. Blow mold processing conditions were adjusted toproduce containers with equivalent distribution of material throughoutthe bottle for each Sample to be submitted for OTR testing. Materialdistribution was characterized by dividing the container into sectionsand weighing each section. Material distribution was also characterizedby measuring the thickness of the container wall using a Hall effectsensor by Magna-Mike Model 8000. Oven power was the primary adjustmentmade to achieve equivalent material distribution for each Sample. Ovenprofile configuration and pre-blow timing were also adjusted in someinstances.

3 bottles per set were mounted and purged with oxygen free gas the dayfollowing blowing and the OTR's of these samples were testedperiodically. Results of these tests are presented in Table 4. FIGS. 2through 4 graphically illustrate portions of the data presented in Table4. As shown in the Figures, each of the bottles made from Concentrate 1over a variety of cobalt concentrations, a variety of polyamidepolymers, and a variety of bulk polyester polymers scavenge oxygen,although those containing about more than 50 ppm cobalt and/or more than1 wt % of the polyamide polymer were more effective. TABLE 4 Days Sample7 Sample 8 Sample 9 Sample 10 Sample 11 Sample 12 Sample 13 Sample 14since OTR OTR OTR OTR OTR OTR OTR OTR blowing (cc/day) # (cc/day) #(cc/day) # (cc/day) # (cc/day) # (cc/day) # (cc/day) # (cc/day) # 70.0463 3 0.0006 2 0.0034 2 0.0381 3 0.0195 2 0.0263 1 −0.0040  1 0.03783 7 — — — — — — — — — — 0.0266 2 — — — — 11 0.0523 2 0.0011 2 0.0006 10.0372 2 — — 0.0274 3 0.0015 2 0.0350 2 11 0.0499 1 0.0013 3 0.0012 3 —— — — — — — — — — 14 — — — — — — 0.0405 1 0.0017 3 — — — — 0.0257 1 14 —— — — — — — — 0.0013 1 — — — — — — 19 — — — — — — — — — — — — 0.0011 3 —— 32 0.0425 2 0.0005 1 0.0006 3 0.0332 3 0.0191 2 0.0054 2 0.0013 1 — —32 0.0502 3 — — — — — — — — — — — — — — 36 — — — — — — — — — — 0.0032 1— — — — 41 0.0280 1 0.0004 2 −0.0001  1 0.0079 1 0.0006 1 0.0019 3 — —0.0035 2 41 — — 0.0012 3 — — — — — — — — — — — — 46 — — — — 0.0014 20.0098 2 0.0003 3 — — 0.0007 1 0.0061 1 46 — — — — — — 0.0355 1 — — — —— — 0.0018 3 53 0.0160 1 0.0009 3 0.0014 1 — — 0.0007 1 0.0018 3 — —−0.0011  2 53 — — — — — — — — 0.0003 3 — — — — — — 64 0.0504 3 0.0006 10.0005 3 — — — — — — 0.0008 2 — — 76 — — — — — — 0.0049 3 — — 0.0009 2 —— 81 0.0038 2 0.0004 2 — — — — 0.0189 2 0.0010 1 0.0007 3 — — 95 — — — —0.0006 2 0.0322 1 — — — — 0.0008 1 0.0017 3 95 — — — — — — — — — — — — —— 0.0010 2 97 0.0024 1 0.0008 3 — — — — — — — — — — — — 103 0.0264 3 — —— — 0.0039 2 0.0006 1 — — 0.0006 3 — — 109 0.0208 3 — — — — 0.0032 20.0005 1 — — 0.0004 3 — — 113 — — 0.0009 1 — — — — 0.0008 3 0.0010 2 — —— — 113 — — — — — — — — — — 0.0023 3 — — — — 120 0.0074 2 0.0004 20.0007 1 0.0145 3 0.0158 2 0.0017 1 0.0003 2 0.0012 1 120 — — — — 0.00083 — — — — — — — — — — 123 0.0049 1 — — — — 0.0085 3 0.0007 3 — — — — — —137 0.0089 2 — — — — 0.0252 1 0.0145 2 — — — — — — 137 0.0079 3 — — — —0.0069 2 0.0005 1 — — — — — — 152 — — — — 0.0034 2 — — — — 0.0022 3 — —0.0007 3 158 — — 0.0006 1 — — — — 0.0006 3 — — 0.0004 1 0.0006 2 158 — —0.0008 3 — — — — — — — — — — — — 165 0.0057 1 — — — — — — — — — — — — —— 165 0.0080 2 — — — — — — — — — — — — — — 187 0.0084 3 — — 0.0007 1 — —— — — — — — — — 268 0.0222 3 0.0011 2 — — — — — — — — — — — — 353 0.02953 0.0005 1 — — — — — — — — — — — — 363 0.0312 1 — — — — — — — — — — — —— — 363 0.0324 2 — — — — — — — — — — — — — —

Example 3

This example demonstrates that solid concentrates are an effective meansfor adding oxidation catalysts to a range of bulk polyester polymercompositions. 25 gram preforms and 20 oz straightwall bottles wereprepared from the following compositions using Solid Concentrate 1.TABLE 5 PA-A target amt Measured Co Sample # Bulk PET (wt %) amount(ppm)* 15 Resin 1 3 101 16 Resin 5 3 95 17 Resin 6 3 86 18 Resin 7 3 93*by XRF.

In Samples 15-18, the source of cobalt was Solid Concentrate 1. Theamount of Solid Concentrate 1 added to the melt processing zone in theinjection molding machine is varied to yield the amounts of cobalt setforth in Table 5. The stream of bulk polyester polymer particles is asset forth in the second column of Table 5. The PA-A was fed to theinjection molding machine as a separate stream of polyamide pellets.

The preforms and bottles are prepared by the following method:

The PA-A was dried at 150 F while the bulk PET resin was dried in aseparate system at 325 F. Solid Concentrate 1 was not dried. Afterdrying but before injection molding, the PA-A, bulk PET, and SolidConcentrate 1 were physically blended using a ribbon mixer. The blendwas fed into a drying hopper with a temperature set point of 325 F,located directly over the feed throat of the injection molding machine.Extruder and manifold temperatures were set at 536 F. Clear preformswere molded using a Husky LX160PET-P60/50-E42 and an 8 cavity, 25 grampreform mold with a 28 mm finish.

Straight wall, 20 oz., carbonated soft drink style containers were blowmolded using a Sidel SBO 2/3 at an output rate of 1200bottles/hour/mold. A water temperature setting of 50 F was used to chillthe blow mold cavities. Blow mold processing conditions were adjusted toproduce containers with equivalent distribution of material throughoutthe bottle for each Sample to be submitted for OTR testing. Materialdistribution was characterized by dividing the container into sectionsand weighing each section. Material distribution was also characterizedby measuring the thickness of the container wall using a Hall effectsensor by Magna-Mike Model 8000. Oven power was the primary adjustmentmade to achieve equivalent material distribution for each Sample. Ovenprofile configuration and pre-blow timing were also adjusted in someinstances.

3 bottles per set were mounted and purged with oxygen free gas the dayfollowing blowing. OTR's of these samples were tested periodically.Results of these tests are presented in Table 6 and in the correspondingFIG. 5, which graphically illustrates the OTR results in Table 6. TABLE6 Sample 15 Sample 16 Sample 17 Sample 18 Days since OTR OTR OTR OTRblow (ccSTP/ (ccSTP/ (ccSTP/ (ccSTP/ molding day) bottle # day) bottle #day) bottle # day) bottle # 4 0.0346 3 0.0016 1 0.0012 3 0.0012 2 4 — —0.0012 2 0.0014 1 0.0017 1 4 — — — — 0.0011 2 — — 8 0.0323 2 0.0010 3 —— 0.0012 3 8 0.0327 1 — — — — — — 11 0.0283 1 — — — — — — 11 0.0237 2 —— — — — — 14 0.0256 1 — — — — — — 14 0.0193 2 — — — — — — 17 0.0142 3 —— — — — — 20 0.0194 1 0.0004 3 0.0003 3 0.0008 1 20 0.0083 3 — — — — — —21 0.0146 2 — — — — — — 24 0.0059 3 — — — — — — 24 0.0113 2 — — — — — —24 0.0174 1 — — — — — — 29 0.0038 3 — — — — — — 29 0.0082 2 — — — — — —29 0.0107 1 — — — — — — 36 0.0064 1 — — — — — — 36 0.0051 2 — — — — — —38 0.0054 1 — — — — — — 38 0.0043 2 — — — — — — 40 0.0037 1 0.0003 10.0007 2 0.0006 2 40 0.0031 2 — — — — — — 40 0.0018 3 — — — — — — 420.0029 1 — — — — — — 50 0.0017 1 — — — — — — 53 0.0012 2 0.0005 1 0.00032 0.0005 2 59 0.0006 3 59 0.0005 1 0.0004 1 0.0012 1 0.0002 3 70 0.00071 0.0010 1 0.0010 1 0.0003 3 80 0.0013 1 — — — — — — 89 0.0004 2 0.00042 0.0006 1 0.0002 2 89 0.0007 3 — — — — — — 96 0.0004 1 0.0006 2 0.00042 0.0004 3 102 −0.0013 2 0.0003 3 0.0006 1 0.0007 1 110 0.0004 1 0.00041 119 0.0006 3 0.0005 2 0.0004 2 0.0003 3 126 0.0003 2 — — — — — — 1260.0006 1 — — — — — — 137 −0.0014 2 0.0024 1 0.0007 1 0.0003 2 150 0.00121 0.0003 3 0.0004 2 0.0003 3 174 0.0007 3 0.0002 3 0.0004 2 0.0003 1 174−0.0016 1 — — — — — — 194 0.0008 1 0.0006 1 0.0008 1 0.0003 3 208 0.00052 — — — — — — 211 0.0003 3 0.0005 2 0.0006 2 0.0005 3 215 0.0005 1 — — —— — — 246 0.0008 1 0.0006 1 0.0009 1 0.0011 1 253 −0.0004 2 0.0009 3 — —— — 260 0.0008 1 — — 0.0012 2 0.0007 2 283 0.0008 3 0.0006 2 — — — —

These examples further demonstrate that PET based cobalt concentratesare effective at catalyzing the oxygen scavenging activity over a rangeof bulk polyester compositions.

Example 4

This example illustrates that the addition of cobalt is not effective asan oxidation catalyst if added to a polyester polymer undergoing meltphase polymerization, whereas if added as a concentrate, the compositionactively scavenges oxygen. 37 gram preforms and 16 oz bottles areprepared using the bulk PET resins listed in Table 7. PA-A is first heattreated. The compositions of these samples are set forth in Table 7.TABLE 7 Approximate Actual Co Level PA-A amt Sample # Bulk PET fromX-ray: (wt %) 19 Resin 8 62 1.2 20 Resin 9 88 1.5 21 Resin 10 68 1.6 22Resin 11 105 1.3

In Samples 19-22, the presence of cobalt in the preforms was solely as aresult of adding cobalt acetate to the melt phase reaction duringpolycondensation for the polymerization of the bulk PET. None of thecobalt present in the sample was added by way of a concentrate. The PA-Awas fed to the injection molding machine as a separate stream ofpolyamide pellets.

Preforms and bottles were prepared and mounted and purged with oxygenfree gas 12 days after blowing. The OTR's of these samples were testedperiodically. Results of these tests are presented in Table 8, andgraphically illustrated in FIG. 6. These comparative examplesdemonstrate that about 60 to 100 ppm cobalt added during the PETpolymerization step is not effective at catalyzing the oxygen scavengingreactions in PET/PA-A blends, even though shown in other foregoingexamples, this same level of cobalt is effective when the cobalt isadded by way of a solid Concentrate. TABLE 8 Sample 19 Sample 20 Sample21 Sample 22 Days since OTR OTR OTR OTR blowing (cc/day) Bottle #(cc/day) Bottle # (cc/day) Bottle # (cc/day) Bottle # 16 — — 0.0305 20.0294 2 0.0258 1 19 0.0353 2 0.0342 3 0.0287 1 0.0315 2 19 0.0349 3 — —— — — — 23 0.0288 2 0.0296 1 0.0291 3 0.0192 3 26 0.0274 2 0.0279 30.0268 2 0.0274 1 26 0.0284 3 — — — — — — 32 0.0328 3 0.0322 2 0.0334 10.0302 2 32 — — — — — — 0.0258 3 39 0.0316 2 0.0322 1 0.0319 3 0.0302 145 0.0360 3 0.0323 3 0.0318 2 0.0294 2 45 — — — — — — 0.0247 3 47 0.02812 0.0286 2 0.0300 1 0.0266 1 61 0.0272 3 0.0274 1 0.0272 3 0.0258 2 730.0259 2 0.0260 3 — — — — 79 — — — — 0.0278 2 0.0163 3 82 0.0305 30.0301 2 0.0307 1 0.0281 1 93 — — — — — — 0.0269 2 98 0.0301 2 0.0315 10.0316 3 — —

Example 5

This example demonstrates that the cobalt added by way of a solidconcentrate is as effective at catalyzing oxygen scavenging reactions ascobalt added by way of a liquid carrier.

48 gram preforms and 1 liter bottles were prepared using Resin 5 as thebulk PET, PA-A pellets added neat, and two different cobalt sources,LIQ1 and Solid Concentrate 2. The composition of the preforms is as setforth in Table 9. TABLE 9 Co PA-A Sample # Source Zn Co Sb P wt % 23LIQ1 60 103 231 76 1.24 24 Conc 2 60 65 231 76 1.99 25 Conc 2 61 97 23277 1.4*by HNMR, metal levels by XRF

The PA-A was fed to the injection molding machine as a separate streamof polyamide pellets. The preforms and bottles are prepared by thefollowing method:

The PA-A was dried at 150 F while the bulk PET resin was dried in aseparate system at 325 F. The solid cobalt Concentrates were driedovernight at 150° F. After drying but before injection molding, thePA-A, bulk PET, and Co Concentrate were physically blended using aribbon mixer. The blend was fed into a drying hopper with a temperatureset point of 325 F, located directly over the feed throat of theinjection molding machine. Extruder and manifold temperatures were setat 536 F. Clear preforms were molded using a Husky LX160PET-P60/50-E42and a 4 cavity, 48 gram preform mold with a 43 mm finish.

One liter heatset containers were blow molded using a Sidel SBO 2/3-HRat an output rate of 1000 bottles/hour/mold. An oil temperature settingof 257 F was used to heat the blow mold cavities. The water heating themold base was set to a target temperature of 176 F. Blow mold processingconditions were adjusted to produce containers with equivalentdistribution of material throughout the bottle for each Sample to besubmitted for OTR testing. Material distribution was characterized bydividing the container into sections and weighing each section. Materialdistribution was also characterized by measuring the thickness of thecontainer wall using a Hall effect sensor by Magna-Mike Model 8000. Ovenpower was the primary adjustment made to achieve equivalent materialdistribution for each Sample. Oven profile configuration and pre-blowtiming were also adjusted in some instances.

3 bottles of each set were mounted and purged with oxygen free gas theday following blowing. OTR's were monitored periodically. The resultsare set forth in Table 10 and graphically illustrated in FIG. 7. TABLE10 Sample 23 Sample 24 Sample 25 Days since OTR OTR OTR blowing (cc/day)Bottle # (cc/day) Bottle # (cc/day) Bottle # 5 0.0574 1 0.0437 1 0.04611 5 — — — — 0.0435 2 8 0.0485 1 0.0138 1 0.0205 1 8 — — — 0.0236 2 120.0290 2 0.0015 2 0.0024 3 12 — — 0.0011 3 — — 15 0.0193 3 0.0015 10.0010 1 15 — — — — 0.0016 2 18 0.0238 1 0.0008 2 0.0006 3 18 0.0020 20.0009 3 — — 22 0.0022 3 — — — — 27 0.0006 1 — — — — 27 0.0020 2 — — — —44 0.0005 3 — — 0.0001 3 47 — — 0.0004 3 — — 110 — — 0.0012 1 — —

The results demonstrate that cobalt added by way of a solid concentrateis at least as effective as cobalt added by way of a liquid carrier. Inaddition, clean up was much quicker with the samples prepared usingsolid concentrates, as the liquid carriers left a residue on theequipment used to blend and feed the pellets to the injection moldingmachine. This residue had to be physically removed so that it did notcontaminate the machine for future use. This cleaning was timeconsuming. In contrast, any remaining pellets of the solid concentratescould be quickly removed by brushing or using compressed air to blow thesolid concentrate off of the equipment. In addition, spills of liquidconcentrate outside the blending and feed equipment presented the sameclean up issues, while spills of the solid concentrate were again mucheasier to move. Since spills and formulation changes are to be expectedin a manufacturing operation, this represents a significant advantagefor the solid concentrate.

Example 6

This example illustrates the effectiveness of solid concentrates atreducing haze relative to the addition of cobalt added by way of aliquid carrier. 25 gram preforms and 20 oz straightwall bottles wereprepared from the compositions set forth in Table 11. TABLE 11 SampleBulk PET Co Source Co level (ppm) PA-A wt % 26 Resin 12 Conc 1 103 1.2327 Resin 4 Conc 1 126 1.39 28 Resin 5 Conc 1 113 1.31 29 Resin 5 LIQ2101 1.33

PA-A was added neat as a separate stream of pellets. The preforms weremade by the following method:

The PA-A was used as received from an unopened bag without furtherdrying while the bulk PET resin was dried in a separate system at 325 F.None of the cobalt Concentrates were dried. After drying but beforeinjection molding, the PA-A, bulk PET, and Co Concentrate werephysically blended using a ribbon mixer. The blend was fed into a dryinghopper with a temperature set point of 325 F, located directly over thefeed throat of the injection molding machine. Extruder and manifoldtemperatures were set at 536 F. Clear preforms were molded using a HuskyLX160PET-P60/50-E42 and an 8 cavity, 25 gram preform mold with a 28 mmfinish.

Straight wall, 20 oz., carbonated soft drink style containers were blowmolded using a Sidel SBO 2/3 at an output rate of 1200bottles/hour/mold. A water temperature setting of 50 F was used to chillthe blow mold cavities. Blow mold processing conditions were adjusted toproduce containers with equivalent distribution of material throughoutthe bottle for each Sample to be submitted for OTR testing. Materialdistribution was characterized by dividing the container into sectionsand weighing each section. Material distribution was also characterizedby measuring the thickness of the container wall using a Hall effectsensor by Magna-Mike Model 8000. Oven power was the primary adjustmentmade to achieve equivalent material distribution for each Sample. Ovenprofile configuration and pre-blow timing were also adjusted in someinstances.

Sidewalls were cut from these bottles and mounted on Mocon Oxtran 1000instruments 3 days after blowing. On the instruments one side of thesidewall was swept with humidified oxygen free carrier gas and the otherside was swept with humidified breathing quality air and the apparentsidewall permeability (the oxygen flux through the sidewall, times theaverage thickness of the sidewall, divided by the driving force forpermeation) was monitored over time. Samples were maintained at 23°C.±1° C. for the duration of the test.

These results (in cc(STP) mil/100 in²/day/atm) are presented in Table 12and the results for days 4 through 98 days after blowing are graphicallyillustrated in FIG. 8. As can be seen from FIG. 8, all samples scavengedoxygen, as at time greater than about 5 days after blowing through theend of the test, the apparent oxygen permeability for all Samples isless than 4, which is the approximate value for PET sidewalls preparedunder the same conditions. TABLE 12 Apparent permeabilities(cc(STP)mil/100 in²/day/atm) Days since blowing Sample 26 Sample 27Sample 28 Sample 29 3 8.48 4.43 6.14 8.40 4 4.10 2.33 3.00 4.09 5 3.591.54 2.20 3.32 6 3.71 0.63 1.03 3.07 7 3.53 0.28 0.30 2.62 8 3.48 0.100.01 2.26 9 3.42 0.03 −0.02 1.24 10 3.32 0.02 −0.02 0.81 11 3.26 0.02−0.01 0.58 14 2.86 0.02 0.01 0.08 18 2.14 0.02 0.03 0.03 21 1.69 0.010.00 0.00 24 1.37 −0.01 −0.03 −0.02 31 0.91 0.01 −0.02 −0.01 38 0.760.03 0.02 0.01 42 0.63 −0.02 −0.02 −0.04 46 0.54 0.02 0.04 0.01 49 0.490.00 −0.02 −0.02 56 0.33 −0.03 −0.02 −0.02 64 0.17 −0.03 −0.03 −0.02 720.13 −0.03 −0.01 −0.01 81 0.09 −0.01 0.04 −0.02 88 0.07 0.12 0.08 −0.0198 0.10 0.03 0.01 0.01

The haze levels for sidewalls of each sample were also measuredaccording to ASTM D-1003 using a Gardner Haze meter. The haze result forSample 26 was 2.6%; for Sample 27 was 2.8%, for Sample 28 was 3.65%, andfor Sample 29 was 6.04%. Each of these values represents the average ofthree sidewalls. The sample containing the cobalt added by way of aliquid carrier has the highest haze at comparable cobalt and polyamideloadings, while preforms and bottles containing cobalt added by way of asolid concentrate have reduced haze levels.

Example 7

This example illustrates the effect of liquid carriers and solidconcentrates on volatility and changes in viscosity. 48 gram preformsand 1 liter bottles were prepared using Resin 5 as the bulk PET, PA-Aand four different cobalt sources: LIQ1, LIQ 2, Solid Concentrate 1 andSolid Concentrate 2. The preform compositions contained the amounts ofcobalt and polyamide as set forth in Table 13. TABLE 13 Co level bySample # Co Source X-ray (ppm) PA-A 30 LIQ1 113 1.4 31 LIQ2 135 1.4 32Solid 1 125 1.2 33 Solid 2 116 1.3

LIQ1 was no longer free flowing at room temperature (˜9 months afterreceipt.) In addition, when LIQ2 was added to the warm pellets of Resin5 bulk PET and PA-A, considerable quantities of volatiles were generatedthat produced an objectionable odor. Changes in viscosity and generationof volatiles are both undesirable in a preform manufacturing operation.No such changes in viscosity or volatiles were noted with the solidConcentrates.

Preforms were made by the following procedure: The PA-A was dried at 150F while the bulk PET resin was dried in a separate system at 325 F. Noneof the cobalt Concentrates were dried. After drying but before injectionmolding, the PA-A, bulk PET, and Co Concentrate were physically blendedusing a ribbon mixer. The blend was fed into a drying hopper with atemperature set point of 325 F, located directly over the feed throat ofthe injection molding machine. Extruder and manifold temperatures wereset at 536 F. Clear preforms were molded using a HuskyLX160PET-P60/50-E42 and a 4 cavity, 48 gram preform with a 43 mm finish.

One liter heatset containers were blow molded using a Sidel SBO 2/3-HRat an output rate 1000 bottles/hour/mold. An oil temperature setting of257 F was used to heat the blow mold cavities. The water heating themold base was set to a target temperature of 176 F. Blow mold processingconditions were adjusted to produce containers with equivalentdistribution of material throughout the bottle for each Sample to besubmitted for OTR testing. Material distribution was characterized bydividing the container into sections and weighing each section. Materialdistribution was also characterized by measuring the thickness of thecontainer wall using a Hall effect sensor by Magna-Mike Model 8000. Ovenpower was the primary adjustment made to achieve equivalent materialdistribution for each Sample. Oven profile configuration and pre-blowtiming were also adjusted in some instances.

Bottles stretch blow molded from the preforms were mounted and purgedwith oxygen free gas 1 day after blowing and OTR's were measuredperiodically. Results are set forth in Table 14 and graphicallyillustrate in FIG. 9. The results show that all samples scavenged oxygenat acceptable rates. TABLE 14 Sample 30 Sample 31 Sample 32 Sample 33Days since OTR OTR OTR OTR blowing (cc/day) bottle # (cc/day) bottle #(cc/day) bottle # (cc/day) bottle # 6 0.0587 1 0.0561 1 0.0517 1 0.05783 6 0.0516 2 0.0468 2 0.0544 3 0.0536 1 13 0.0497 3 0.0240 3 0.0281 20.0568 2 17 0.0478 1 0.0132 1 0.0106 1 0.0487 1 23 — — 0.0025 2 — — — —26 0.0208 2 — — 0.0138 3 0.0446 3 31 0.0034 3 0.0016 3 0.0005 2 0.0364 239 0.0058 1 — — 0.0009 1 0.0130 1 56 0.0006 2 — — — — 0.0030 3

Example 8

This example illustrates the superior color properties in b*, L*, andYellowness Index (Y1) in bottles made with concentrates relative tobottles made with liquid carriers. This example also demonstrates thesuperior color property in b* and Yl in bottles made from concentrateswhich are co-dried relative to bottles made with liquid concentrates inwhich the polyamide and polyester particles are individually dried.

25.6 gram preforms were produced on a BOY 22S injection molding machineusing a single preform cavity mold. In all samples, Resin 5 pellets,PA-A pellets, and a cobalt source were fed to the injection moldingmachine in the measured amounts and by the type of cobalt source asshown in Table 15. Samples 34 through 43 were mixed after drying thepolyamide and PET resin and prior to addition to the hopper of the BOY22S. Samples 44 and 45 were mixed prior to drying. TABLE 15 Co Metals byX-ray (ppm) HNMR Sample # Source Zn: Co: Mn: Ti: Sb: P: PA-A wt %: 34Solid 57 43 1 1 221 72 1.39 Conc 1 35 Solid 57 95 1 1 223 76 1.24 Conc 136 Solid 57 186 3 1 221 79 1.38 Conc 1 37 Solid 58 46 0 0 224 72 1.01Conc 2 38 Solid 59 91 −1 0 225 72 1.43 Conc 2 39 Solid 59 172 0 0 220 731.42 Conc 2 40 LIQ2 58 47 −1 0 220 72 1.55 41 LIQ2 59 103 −1 0 221 721.55 42 LIQ2 59 108 0 0 220 71 1.43 43 LIQ2 58 204 0 0 220 72 1.72  44*Solid 56 103 1 0 222 76 1.30 Conc 1  45* Solid 58 89 −1 0 222 74 1.29Conc 2*all components dried at PET conditions prior to molding, componentsdried separately for other samples.

The preforms and bottles were made by the following procedure:

For the samples that were prepared without codrying, the PA-A was driedat 60° C. while the bulk PET resin was dried in a separate system at168° C. and the cobalt concentrates were not dried. After drying, butbefore injection molding, the PA-A, bulk PET, and Co Concentrate werephysically paddle blended by hand. The mixture was fed into a hopper,located directly over the feed throat of the injection molding machine.Extruder and manifold temperatures were set at 270 C. Clear preformswere molded using a BOY Model 22D and a 1 cavity, 25.6 gram preform witha 28 mm finish.

For the samples that were codried prior to injection molding, the PA-A,PET and solid cobalt Concentrates were mixed same as above and thendried at 168° C. for 8 hrs. Following drying, the mixture was fed into ahopper, located directly over the feed throat of the BOY Model 22Dinjection molded machine and preforms were produced as described above.

Color measurements for the preforms were taken and the results arereported in Table 16. TABLE 16 Avg. Avg. Avg. Avg. Avg. Sample # Sampledescription L*: a*: b* YI: WI: Co @50 ppm 34 Solid Conc 1 72.03 −1.08−1.62 −5.04 52.94 37 Solid Conc 2 73.27 −1.28 −0.97 −3.60 51.09 40 LIQ271.26 −1.38 1.64 2.64 33.06 Co @100 ppm 35 Solid Conc 1 68.61 −0.87−3.73 −10.63 61.04 38 Solid Conc 2 70.58 −1.17 −2.34 −7.06 55.18 41, 42LIQ2 66.02 −0.42 2.99 7.23 16.94 (Avg.) Co @200 ppm 36 Solid Conc 165.37 0.71 −7.74 −20.84 82.06 39 Solid Conc 2 64.71 0.15 −5.78 −15.9569.72 43 LIQ2 53.17 1.50 5.33 17.69 −17.41 Codried (Co @ 100 ppm) 44Solid Conc 1 69.04 −1.18 −0.14 −1.56 40.25 45 Solid Conc 2 69.28 −1.31−1.01 −3.92 45.79 Control NA No Conc, PA 79.36 −1.03 3.00 5.70 39.65

The results indicate that the preforms made with solid concentratesexhibit better color than preforms made with liquid carriers atequivalent loadings of cobalt, as shown by the lower b*, lower Yl, andhigher L* values of the preforms made with concentrates. Compare Samples34-39 with Samples 40-43.

A comparison of Samples 44 and 45 against 41 and 42 indicates that thecolor of preforms in which all components were “codried” (dried togetherprior to injection molding), had better visual appearance and colorvalues than preforms in which the pellets streams were individuallydried and cobalt was added as a liquid concentrate at similar cobalt andpolyamide loadings.

Preforms corresponding to Samples 35, 38, 44 and 45 were ground througha 3 mm screen and 1 gram samples were loaded into 20 ml prescored glassampoules (Wheaton #176782) containing an OxyDot (OxySense Inc., 1311North Central Expressway Suite 44, Dallas, Tex. 75243, USA) glued on theside of the ampoule with silicon adhesive. Two such ampoules wereprepared for each Sample tested. These ampoules were then sealed andplaced in an oven maintained at 75° C. The partial pressure of oxygen ineach of the ampoules (PO₂) was then monitored periodically using anOxySense instrument (OxySense Inc.) to assess the oxygen scavengingperformance of the compositions. The results are graphically illustratedin FIG. 10.

As shown in FIG. 10, the codrying process surprisingly improves thescavenging performance of the Samples as indicated by the lower PO₂ forthe codried samples in this OxySense test.

Thus, codrying the bulk PET, polyamide pellets, and the concentratesimproved the oxygen scavenging characteristics of the preforms whilemaintaining better color in terms of b* color, L* color, Yl than thesamples prepared with a liquid concentrate.

Example 9

LIQ2 was stored for approximately 12 weeks at laboratory conditions.Gradations in consistency of the dispersion were evident. Changes inconsistency over time, whether due to settling of the cobalt salt orother causes, would complicate manufacturing procedures using thedispersion. No such variations were noted after storage of polyesterbased Solid Concentrates 1 and 2.

Example 10

This example demonstrates the improved capability of compounding highlevels of cobalt into polymers of increasing cyclohexane dimethanol(CHDM) levels. This example demonstrates that the metal loading can beraised in a commercial manufacturing scaleable process.

Different levels of cobalt neodecanoate were melt blended into polyesterpolymers or polymer mixtures of increasing levels of CHDM in a pilotscale 57 mm twin-screw extruder according to the attached table.Separate feeds of polyester polymer resin and resin mixtures and cobaltneodecanoate, in the form of a pastel and supplied as Cobalt Ten-Cem22.5% from OMG (22.5% of the Cobalt Ten-Cem represents the amount byweight of cobalt), were fed into a twin-screw and melt blended at a setpoint of approximately 235° C. Molten polymer exited the extruder in theform of approximate 0.08″ diameter strands which are water quenched andcut into approximate 0.125″ length pellets. 50-200 lbs of eachcomposition were extruded and qualitative judgments were made about theability to strand and cut each material. Polyester polymer resins withthe higher amount of CHDM modification processed the best at the higherloadings of cobalt neodecanoate. The reported amounts are based on theweight of the compound. The weight of the cobalt content can becalculated by multiplying the cobalt neodecanoate compound weight by0.225.

Sample 46: 97.78% Polyester Polymer Resin 3; 2.22 wt. % cobaltneodecanoate; CHDM content of the polyester=3.5 mole %

-   -   Results: brittle strands, a few “sticks” as strands shattered in        the cutter. Sticks are referred to herein as strands which were        cut into pieces longer than the typical ⅛″ pellet.

Sample 47: 96.33% Polyester Polymer Resin 3; 3.67 wt. % cobaltneodecanoate; CHDM content of the polyester=3.5 mole %

-   -   Results: brittle strands, lots of “sticks”

Sample 48: 96.33% Polyester Polymer Resin 13: 3.67% cobalt neodecanoate;CHDM content of the polyester=4.5 mole %

-   -   Results: brittle strands, lots of “sticks”, slightly better than        Sample 47

Sample 49: 70.40% Polyester Polymer Resin 13 and 27.38% PolyesterPolymer Resin 14; 2.22 wt. % cobalt neodecanoate; CHDM content of theresulting polyester=11 mole %

-   -   Results: brittle strands, “sticks”

Sample 50: 70.40% Polyester Polymer Resin 3 and 27.38% Polyester PolymerResin 14; 2.22 wt. % cobalt neodecanoate; % CHDM content of theresulting polyester=11 mole %

-   -   Results: brittle strands, “sticks”

Sample 51: f 69.36% Polyester Polymer Resin 3 and 26.97% PolyesterPolymer Resin 14; 3.67 wt. % cobalt neodecanoate; CHDM content of theresulting polyester=11 mole %

-   -   Results: brittle strands, “sticks”

Sample 52: 96.33% Polyester Polymer Resin 14; 3.67 wt. % cobaltneodecanoate; CHDM content of the polyester=31 mole %

-   -   Results: not as brittle, no sticks, ran better

Sample 53: production of 4300 lbs of 96.33% Polyester Polymer Resin 15(31 mole % CHDM) containing 3.67 wt. % cobalt neodecanoate on a 92 mmtwin-screw extruder.

-   -   Results: ran well enough to qualify for high volume commercial        scale production runs, with few sticks present.

1. A process for the manufacture of a preform comprising: combining (i)solid polyester particles comprising a polyester polymer; (ii) solidpolyamide particles comprising a polyamide polymer; and (iii) solidconcentrate particles comprising: (A) a transition metal provided in anoxidation state other than zero and in an amount of 1,000 ppm to 40,000ppm (by metal), based upon the weight of the concentrate: and (B)polyester polymers in an amount of at least 40 wt. %, based on theweight of the concentrate, wherein at least a portion of the polyesterpolymers comprise highly modified polyester polymers containing (a)polycarboxylic acid modifier residues in an amount ranging from 20 mole% to 60 mole %; and/or (b) hydroxyl modifier residues in an amountranging from 20 mole % to 60 mole % based on 100 mole percent of thepolycarboxylic acid residues and 100 mole percent hydroxyl residues inthe polyester polymer into a melt processing zone, forming a melt, andforming a preform directly from the melt.
 2. The process of claim 1,wherein the transition metal content ranges from 1,000 ppm to 20,000ppm.
 3. The process of claim 2, wherein the transition metal contentranges from 2,000 ppm to 10,000 ppm.
 4. The process of claim 3, whereinthe transition metal content ranges from 3,000 ppm to 8,000 ppm.
 5. Theprocess of claim 1, wherein the transition metal comprises cobalt,copper, rhodium, platinum, rhenium, ruthenium, palladium, tungsten,osmium, cadmium, silver, tantalum, hafnium, vanadium, titanium,chromium, nickel, zinc, or manganese.
 6. The process of claim 1, whereinthe transition metal is provided as a compound comprising a carboxylate,oxide, borate, carbonate, chloride, sioxide, hydroxide, nitrate,phosphate, sulfate, silicate, or mixtures thereof.
 7. The process ofclaim 6, wherein the carboxylate comprises neodecanoates, octanoates,acetates, lactates, naphthalates, malates, stearates, acetylacetonates,linoleates, oleates, palmitates, 2-ethylhexanoates, or ethyleneglycolates.
 8. The process of claim 5, wherein the transition metalcomprises cobalt.
 9. The process of claim 8, wherein the transitionmetal is provided as a compound comprising cobalt neodecanoate, cobaltacetate, or mixtures thereof.
 10. The process of claim 9 wherein thetransition metal is present in an amount ranging from 2,000 ppm to 8,000ppm (by metal) based on the weight of the concentrate.
 11. The processof claim 1, wherein the portion of highly modified polyester polymers isat least 75 wt. % based on the total weight of all polyester polymerspresent in the concentrate.
 12. The process of claim 1, wherein thepolyester polymer contained in the polyester particles and/or the highlymodified polyester polymers contained in the concentrate particlescomprise repeating units of terephthalic acid residues, isophthalic acidresidues, naphthalienic acid residues, or mixtures thereof.
 13. Theprocess of claim 1, wherein said highly modified polyester polymers areobtained by copolymerizing polycarboxylic acid compounds with a hydroxylcompound and a hydroxyl modifier, such that the polymer containshydroxyl modifier residues in an amount of at least 25 mole %, based onthe moles of hydroxyl compound residues present in the polymer.
 14. Theprocess of claim 13, wherein the amount of hydroxyl modifier residuesranges from 30 mole % to 60 mole %, based on all hydroxyl residuespresent in the polymer.
 15. The process of claim 1, wherein thepolyester polymer contained in the polyester particles comprises: (i) apolycarboxylic acid component comprising at least 92 mole % residues ofterephthalic acid, derivates of terephthalic acid, or mixtures thereof,and (ii) a hydroxyl component comprising at least 40 mole % residues ofethylene glycol; and/or the highly modified polyester polymer containedin the concentrate particles comprises: (i) a polycarboxylic acidcomponent comprising at least 92 mole % residues of terephthalic acid orderivates of terephthalic acid or mixtures thereof, and (ii) a hydroxylcomponent comprising at least 40 mole % residues of ethylene glycol andat least 25 mole % and up to 60 mole % residues of a hydroxyl modifier;each based on 100 mole percent of the polycarboxylic acid residues and100 mole percent hydroxyl residues in the polyester polymer.
 16. Theprocess of claim 1, wherein the hydroxyl modifier residue comprises aresidue of butanediol, 1,4-cyclohexane dimethanol,2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, trimethylene glycol,neopentyl glycol, or diethylene glycol or combinations thereof.
 17. Theprocess of claim 16, wherein the hydroxyl modifier residue comprises aresidue of 1,4-cyclohexane dimethanol.
 18. The process of claim 1,wherein the concentrate is essentially free of a polyamide polymer. 19.The process of claim 1, wherein the It.V. of the polyester polymercontained in the polyester particles and/or the It.V. of the highlymodified polyester polymer provided to make the concentrate is from 0.60dL/g to 1.15 dL/g and is obtained without solid state polymerization.20. The process of claim 19, wherein the It.V. of the polyester polymercontained in the polyester particles and/or the It.V. of the highlymodified polyester polymer provided to make the concentrate is at least0.70 dL/g.
 21. The process of claim 1, wherein the concentrate particleshave an It.V. ranging from 0.60 dL/g to 1.15 dL/g.
 22. The process ofclaim 21, wherein the concentrate particles have an It.V. of at least0.70 dL/g.
 23. The process of claim 1, wherein the polyester polymercontained in the polyester particles and/or the highly modifiedpolyester polymer contained in the concentrate is semicrystalline. 24.The process of claim 1, wherein the polyester polymer contained in thepolyester particles and/or the highly modified polyester polymercontained in the concentrate is essentially amorphous and has a DSC Tgof at least 70° C.
 25. The process of claim 1, wherein the transitionmetal is added into a melt phase process for making the highly modifiedpolyester polymer.
 26. The process of claim 1, wherein the concentrateis obtained by melt compounding the highly modified polyester polymerwith the transition metal.
 27. The process of claim 1, wherein thepreform comprises a bottle preform having a composition comprising from1 to 10 wt. % of an oxidizable polymer or an oxygen scavenging polymer,30 to 300 ppm cobalt, and polyester polymer present in an amount of atleast 90 wt. %, each based on the weight of the preform.
 28. The processof claim 27, wherein the preform comprises a bottle preform having acomposition comprising from 50 to 200 ppm cobalt.
 29. The process ofclaim 27, wherein the preform comprises a bottle preform having acomposition comprising from 1 to 5 wt. % of an oxidizable polymer or anoxygen scavenging polymer.
 30. The process of claim 29, wherein thepreform comprises a bottle preform having a composition comprising from50 to 200 ppm cobalt.
 31. The process of claim 1, wherein the let downratio of the transition metal concentration in the concentrate to thetransition metal concentration in the preform composition ranges from30:1 to 200:1.
 32. The process of claim 31, wherein the let down ratioof the transition metal concentration in the concentrate to thetransition metal concentration in the preform composition ranges from30:1 to 100:1.
 33. The process of claim 1, wherein the preform comprisesthe transition metal present in an amount ranging from 30 ppm to 500 ppmbased on the weight of the preform.
 34. The process of claim 33, whereinthe preform comprises the transition metal present in an amount rangingfrom 50 ppm to 300 ppm based on the weight of the preform.
 35. Theprocess of claim 1, wherein the preform further comprises zinc.
 36. Theprocess of claim 35, wherein the zinc is present in the range of from 50ppm to 300 ppm.
 37. The process of claim 36, wherein the zinc is presentin the range of from 50 ppm to 150 ppm.
 38. The process of claim 1,wherein the oxidizable polymer comprises a polyamide polymer havingrepeating units with a benzylic hydrogen atom.
 39. The process of claim38, wherein the polyamide polymer is obtained from a reactant containinga xylylene moiety.
 40. The process of claim 1, wherein the polyamidepolymer has a number average molecular weight Mn of 1,000 to 45,000. 41.The process of claim 40, wherein the polyamide polymer has a numberaverage molecular weight Mn of at least 3,500.
 42. The process of claim41, wherein the polyamide polymer has a number average molecular weightMn of less than 15,000.
 43. The process of claim 1, wherein thepolyester polymer particles, the concentrate particles, and thepolyamide polymer particles are combined into the melt processing zoneas individual streams, as particle/particle dry blends, or ascombinations thereof.
 44. The process of claim 1, further comprisingcombining an additive comprising a colorant, acetaldehyde scavenger,reheat agent, UV absorber or inhibitor, stabilizer, thermal stabilizer,or mixtures thereof.
 45. The process of claim 1, wherein the concentratecontains a higher concentration of the transition metal than present inthe preform.
 46. The process of claim 1, wherein neither the solidpolyester polymer particles nor the polyester polymer used to preparethe concentrate are solid stated.
 47. The process of claim 1, furthercomprising forming a bottle from the preform, wherein the preformcomprises 150 ppm or less of cobalt based upon the weight of thepreform, and wherein the bottle has a sidewall haze of 4.0% or less. 48.The process of claim 47, wherein the bottle has a sidewall haze of 3.5%or less.
 49. A process for the manufacture of a preform comprising:combining (i) solid polyester particles comprising a polyester polymercomprising; (a) polycarboxylic acid component residues comprising atleast 80 mole % residues of terephthalic acid, or derivates ofterephthalic acid, or mixtures thereof; (b) hydroxyl component residuescomprising at least 40 mole % ethylene glycol; based on 100 mole percentof the polycarboxylic acid residues and 100 mole percent hydroxylresidues in the polyester polymer; (ii) solid polyamide particlescomprising a polyamide polymer; and (iii) solid concentrate particlescomprising: (A) a transition metal provided in an oxidation state otherthan zero and in an amount of 1,000 ppm to 40,000 ppm, based upon theweight of the concentrate: and (B) polyester polymers in an amount of atleast 80 wt. %, based on the weight of the concentrate, wherein at least50 wt % of the polyester polymers comprise highly modified polyesterpolymers containing (a) polycarboxylic acid component residuescomprising at least 80 mole % residues of terephthalic acid, orderivates of terephthalic acid, or mixtures thereof; (b) hydroxylcomponent residues comprising at least 40 mole % ethylene glycol, withat least 20 mole % to 60 mole % of residues of a hydroxyl modifier basedon 100 mole percent of the polycarboxylic acid residues and 100 molepercent hydroxyl residues in the polyester polymer; and (C) wherein theconcentrate is free of polyamide polymer; into a melt processing zone,forming a melt, and forming a preform directly from the melt.
 50. Theprocess of claim 49, wherein the transition metal content ranges from1,000 ppm to 20,000 ppm.
 51. The process of claim 50, wherein thetransition metal content ranges from 2,000 ppm to 10,000 ppm.
 52. Theprocess of claim 51, wherein the transition metal comprises cobalt,copper, rhodium, platinum, rhenium, ruthenium, palladium, tungsten,osmium, cadmium, silver, tantalum, hafnium, vanadium, titanium,chromium, nickel, zinc, or manganese.
 53. The process of claim 49,wherein the transition metal is provided as a compound comprising acarboxylate, oxide, borate, carbonate, chloride, sioxide, hydroxide,nitrate, phosphate, sulfate, silicate, or mixtures thereof.
 54. Theprocess of claim 53, wherein the carboxylate comprises neodecanoates,octanoates, acetates, lactates, naphthalates, malates, stearates,acetylacetonates, linoleates, oleates, palmitates, 2-ethylhexanoates, orethylene glycolates.
 55. The process of claim 52, wherein the transitionmetal comprises cobalt.
 56. The process of claim 55, wherein thetransition metal is provided as a compound comprising cobaltneodecanoate, cobalt acetate, or mixtures thereof.
 57. The process ofclaim 49, wherein the portion of highly modified polyester polymers isat least 75 wt. % based on the total weight of all polyester polymerspresent in the concentrate.
 58. The process of claim 49, wherein thehighly modified polyester polymers are obtained by copolymerizingpolycarboxylic acid compounds with a hydroxyl compound and a hydroxylmodifier, such that the polymer contains hydroxyl modifier residues inan amount of at least 25 mole %, based on the moles of hydroxyl compoundresidues present in the polymer.
 59. The process of claim 58, whereinthe amount of hydroxyl modifier residues ranges from 30 mole % to 60mole %, based on all hydroxyl residues present in the polymer.
 60. Theprocess of claim 49, wherein the hydroxyl modifier residue comprises aresidue of butanediol, 1,4-cyclohexane dimethanol,2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, trimethylene glycol,neopentyl glycol, or diethylene glycol or combinations thereof.
 61. Theprocess of claim 60, wherein the hydroxyl modifier residue comprises aresidue of 1,4-cyclohexane dimethanol.
 62. The process of claim 49,wherein the It.V. of the polyester polymer contained in the polyesterparticles and/or the It.V. of the highly modified polyester polymerprovided to make the concentrate is from 0.60 dL/g to 1.15 dL/g and isobtained without solid state polymerization.
 63. The process of claim62, wherein the It.V. of the polyester polymer contained in thepolyester particles and/or the It.V. of the highly modified polyesterpolymer provided to make the concentrate is at least 0.70 dL/g.
 64. Theprocess of claim 49, wherein the concentrate particles have an It.V.ranging from 0.60 dL/g to 1.15 dL/g.
 65. The process of claim 64,wherein the concentrate particles have an It.V. of at least 0.70 dL/g.66. The process of claim 49, wherein the polyester polymer contained inthe polyester particles and/or the highly modified polyester polymercontained in the concentrate is semicrystalline.
 67. The process ofclaim 49, wherein the polyester polymer contained in the polyesterparticles and/or the highly modified polyester polymer contained in theconcentrate is essentially amorphous and has a DSC Tg of at least 70° C.68. The process of claim 49, wherein the transition metal is added intoa melt phase process for making the highly modified polyester polymer.69. The process of claim 49, wherein the concentrate is obtained by meltcompounding the highly modified polyester polymer with the transitionmetal.
 70. The process of claim 49, wherein the preform comprises abottle preform having a composition comprising from 1 to 10 wt. % of anoxidizable polymer or an oxygen scavenging polymer, 30 to 300 ppmcobalt, and polyester polymer present in an amount of at least 90 wt. %,each based on the weight of the preform.
 71. The process of claim 70,wherein the preform comprises a bottle preform having a compositioncomprising from 50 to 200 ppm cobalt.
 72. The process of claim 70,wherein the preform comprises a bottle preform having a compositioncomprising from 1 to 5 wt. % of an oxidizable polymer or an oxygenscavenging polymer.
 73. The process of claim 72, wherein the preformcomprises a bottle preform having a composition comprising from 50 to200 ppm cobalt.
 74. The process of claim 49, wherein the let down ratioof the transition metal concentration in the concentrate to thetransition metal concentration in the preform composition ranges from30:1 to 200:1.
 75. The process of claim 74, wherein the let down ratioof the transition metal concentration in the concentrate to thetransition metal concentration in the preform composition ranges from30:1 to 100:1.
 76. The process of claim 49, wherein the preformcomprises the transition metal present in an amount ranging from 30 ppmto 500 ppm based on the weight of the preform.
 77. The process of claim76, wherein the preform comprises the transition metal present in anamount ranging from 50 ppm to 300 ppm based on the weight of thepreform.
 78. The process of claim 49, wherein the preform furthercomprises zinc.
 79. The process of claim 78, wherein the zinc is presentin the range of 50 ppm to 300 ppm.
 80. The process of claim 79, whereinthe zinc is present in the range of 50 ppm to 150 ppm.
 81. The processof claim 49, wherein the oxidizable polymer comprises a polyamidepolymer having repeating units with a benzylic hydrogen atom.
 82. Theprocess of claim 81, wherein the polyamide polymer is obtained from areactant containing a xylylene moiety.
 83. The process of claim 49,wherein the polyamide polymer has a number average molecular weight Mnof 1,000 to 45,000.
 84. The process of claim 83, wherein the polyamidepolymer has a number average molecular weight Mn of at least 3,500. 85.The process of claim 84, wherein the polyamide polymer has a numberaverage molecular weight Mn of less than 15,000.
 86. The process ofclaim 49, wherein the polyester polymer particles, the concentrateparticles, and the polyamide polymer particles are combined into themelt processing zone as individual streams, as particle/particle dryblends, or as combinations thereof.
 87. The process of claim 49, furthercomprising combining an additive comprising a colorant, acetaldehydescavenger, reheat agent, UV absorber or inhibitor, stabilizer, thermalstabilizer, or mixtures thereof.
 88. The process of claim 49, whereinthe concentrate contains a higher concentration of the transition metalthan present in the preform.
 89. The process of claim 49, wherein thetransition metal comprises cobalt neodecanoate or cobalt acetate presentin an amount ranging from 2,000 ppm to 8,000 ppm (by metal) based on theweight of the concentrate.
 90. The process of claim 49, furthercomprising forming a bottle from the preform, wherein the preformcomprises 150 ppm or less of cobalt based upon the weight of thepreform, and wherein the bottle has a sidewall haze of 4.0% or less. 91.The process of claim 90, wherein the bottle has a sidewall haze of 3.5%or less.
 92. A process for the manufacture of a preform comprising:combining (i) solid polyester particles comprising a polyester polymercomprising; (a) polycarboxylic acid component residues comprising atleast 92 mole % residues of terephthalic acid, or derivates ofterephthalic acid, or mixtures thereof; (b) hydroxyl component residuescomprising at least 40 mole % ethylene glycol, based on 100 mole percentof the polycarboxylic acid residues and 100 mole percent hydroxylresidues in the polyester polymer; and (ii) solid polyamide particlescomprising a polyamide polymer; and (iii) solid concentrate polymercomprising: (A) a transition metal provided in an oxidation state otherthan zero and in an amount of 1,000 ppm to 20,000 ppm, based upon theweight of the concentrate: and (B) highly modified polyester polymers inan amount of at least 80 wt. %, based on the weight of the concentrate,comprising: (a) polycarboxylic acid component residues comprising atleast 92 mole % residues of terephthalic acid, or derivates ofterephthalic acid, or mixtures thereof; (b) hydroxyl component residuescomprising at least 40 mole % ethylene glycol, with at least 20 mole %to 60 mole % of residues of 1,4-cyclohexane dimethanol, diethyleneglycol, or mixtures thereof based on 100 mole percent of thepolycarboxylic acid residues and 100 mole percent hydroxyl residues inthe polyester polymer; and (C) wherein the concentrate is free ofpolyamide polymer; into a melt processing zone, forming a melt, andforming a preform directly from the melt.